CN102639575B - The multi-purpose polymer of hydrolysis-stable - Google Patents

The multi-purpose polymer of hydrolysis-stable Download PDF

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Publication number
CN102639575B
CN102639575B CN201080054494.1A CN201080054494A CN102639575B CN 102639575 B CN102639575 B CN 102639575B CN 201080054494 A CN201080054494 A CN 201080054494A CN 102639575 B CN102639575 B CN 102639575B
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monomer
polymer
methyl
ester
acrylate
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CN102639575A (en
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K·塔马里塞尔维
张琰湜
D·S·菲拉
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Lubrizol Advanced Materials Inc
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Lubrizol Advanced Materials Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon

Abstract

The present invention relates to the multi-purpose polymers of hydrolysis-stable, it comprising monomer mixture below by polymerizeing：Methyl (acrylate) (ASMA) monomer or its salt of at least one amino substitution；With at least one non-ionic vinyl (NIV) monomer, wherein the monomer mixture optionally includes one or more in one or more at least one vinyl association (VA) monomers, at least one vinyl surfactant (VS) monomer, and/or at least one polymerizable silicone macromonomer (PSM), and wherein the monomer mixture includes optionally further one or more at least one to be crosslinked (XL) monomers, at least one chain-transferring agent (CTA), and/or one kind at least one polymer stabilizer or more plant.The multi-purpose polymer of the present invention also can be by containing chain-transferring agent or in polymerization technique prepared by the monomer mixture of common other function ingredients.

Description

The multi-purpose polymer of hydrolysis-stable
Technical field
The present invention relates to multi-purpose polymers, are the polymerizate for including monomer mixture below：At least one ammonia Methyl (acrylate) (ASMA) monomer or its salt of base substitution；With at least one non-ionic vinyl (NIV) monomer, wherein The monomer mixture further includes at least one vinyl association (VA) monomer, at least one vinyl surfactant (VS) It is one or more in monomer, and/or at least one polymerizable silicone macromonomer (PSM), and wherein the monomer is mixed Conjunction object includes optionally further at least one crosslinking (XL) monomer, at least one chain-transferring agent (CTA), and/or at least one It is one or more in polymer stabilizer.The multi-purpose polymer of the present invention can also be by containing chain-transferring agent or in polymerization technique It is prepared by the monomer mixture of other common function ingredients.In one embodiment, multi-purpose polymer of the invention is long Time (for example, more than 6 months or longer time) hydrolysis-stable, it is provided in acidic aqueous compositions wonderful Beneficial rheologic behavio(u)r, and it is compatible with cationic materials.The multi-purpose polymer of the present invention can be used for various products, including but It is not limited to, personal care product, health care products, household care products, public organizations and industrial nursing product and industry are answered With.
Background of invention
By the multipurpose copolymer that for example dimethylaminoethyl acrylate methyl base ammonia ethyl ester (DMAEMA) monomer obtains be this field Know.In some applications, this copolymer can have stability problem when being produced by aforementioned monomer.As a result, these polymerize Object has the storage life of difference and starts " unstable " after about 6 months.This both and can cause various logistical problems and not wish The performance of prestige deteriorates.The storage life of these polymer difference be due to include in DMAEMA monomers amine skeleton caused by, hold Easily hydrolyzed in water-bearing media by " inventing a charge against (back-biting) ".The carbonyl of lone pair electrons attack electron deficient on nitrogen-atoms Carbon obtains 5 membered ring zwitterionic intermediates.Then, such structure can be hydrolyzed easily in the presence of water.As shown below is anti- The problem for answering protocol summary related with the copolymer obtained by DMAEMA monomers.Hydrolysis as a result, copolymer skeleton Upper generation-COOH functional sites and dimethylaminoethanol by-product.
In view of the above circumstances, this field needs the hydrolysis-stable for possessing suitable storage life (for example, more than 6 months or longer) Multipurpose copolymer.
Summary of the invention
The present invention relates to multi-purpose polymers, are the polymerizate for including monomer mixture below：At least one ammonia Methyl (acrylate) (ASMA) monomer or its salt of base substitution；With at least one non-ionic vinyl (NIV) monomer, wherein The monomer mixture further includes at least one vinyl association (VA) monomer, at least one vinyl surfactant (VS) It is one or more in monomer, and/or at least one polymerizable silicone macromonomer (PSM), and wherein the monomer is mixed Conjunction object includes optionally further at least one crosslinking (XL) monomer, at least one chain-transferring agent (CTA), and/or at least one It is one or more in the stabilizer of polymerization.The multi-purpose polymer of the present invention can also be by containing chain-transferring agent or in polymerization technique It is prepared by the monomer mixture of common other functional components.In one embodiment, multi-purpose polymer of the invention is long Time (for example, more than 6 months or longer time) hydrolysis-stable, it is provided in acidic aqueous compositions wonderful Beneficial rheologic behavio(u)r, and it is compatible with cationic materials.The multi-purpose polymer of the present invention can be used for various products, including but It is not limited to, personal care product, health care products, household care products, public organizations and industrial nursing product and industry are answered In.
The multi-purpose polymer of the present invention can include suitably that each component described herein, element and technique are described, by it Composition is consisting essentially of.Suitably the present invention of illustrative disclosure can be there is no disclose particularly herein herein Any element in the case of implement.
Unless otherwise indicated, all percentages, number and the ratio expressed herein are all based on the composition of the present invention Total weight, and all wt is all based on 100% active constituent expression.
In one embodiment, the present invention relates to the polymer of hydrolysis-stable, for comprising monomer (a), (b), and appoint Selection of land includes the reaction product of the monomer mixture selected from (c), (d), (e), (f), (g), (h) and its component in mixture.
In another embodiment, the present invention relates to the polymer of hydrolysis-stable, and the list of following monomer is included for polymerization The reaction product of body mixture：
(i) (a), (b) and (c)；
(ii) (a), (b) and (d)；
(iii) (a), (b) and (e)；
(iv) (a), (b), (c) and (d)；
(v) (a), (b), (c) and (e)；
(vi) (a), (b), (d) and (e)；Or
(vii) (a), (b), (c), (d) and (e),
Wherein (a) is methyl (acrylate) (ASMA) monomer or its salt of at least one amino substitution；(b) it is at least one Non-ionic vinyl (NIV) monomer of kind；(c) it is at least one vinyl association (VA) monomer；(d) it is at least one vinyl Surfactant (VS) monomer；(e) it is at least one polymerizable silicone macromonomer (PSM)；It is above-mentioned with any of which Mixture includes optionally further：(f) at least one crosslinking (XL) monomer；(g) at least one chain-transferring agent (CTA)；(h) extremely A kind of few polymer stabilizer；Or component (f), (g) and/or (h) in any suitable combination of two or more.
In another embodiment, the present invention relates to the polymer of hydrolysis-stable, mixed for the monomer comprising following monomer Close the reaction product of the polymerization of object：
(i) (a), (b) and (c)；
(ii) (a), (b) and (d)；
(iii) (a), (b) and (e)；
(iv) (a), (b), (c) and (d)；
(v) (a), (b), (c) and (e)；
(vi) (a), (b), (d) and (e)；Or
(vii) (a), (b), (c), (d) and (e),
Wherein (a) is methyl (acrylate) (ASMA) monomer or its salt of at least one amino substitution；(b) it is at least one Non-ionic vinyl (NIV) monomer of kind；(c) it is at least one vinyl association (VA) monomer；(d) it is at least one vinyl Surfactant (VS) monomer；(e) it is at least one polymerizable silicone macromonomer (PSM)；It is above-mentioned with any of which Mixture further includes：(f) at least one crosslinking (XL) monomer；(g) at least one chain-transferring agent (CTA)；(h) at least one The stabilizer of polymerization；Or component (f), (g) and/or (h) in any suitable combination of two or more.
In yet another embodiment, the present invention relates to the polymer of hydrolysis-stable, mixed for the monomer comprising following monomer Close the reaction product of the polymerization of object：
(i) (a), (b) and (c)；
(ii) (a), (b) and (d)；
(iii) (a), (b) and (e)；
(iv) (a), (b), (c) and (d)；
(v) (a), (b), (c) and (e)；
(vi) (a), (b), (d) and (e)；Or
(vii) (a), (b), (c), (d) and (e),
Wherein (a) is methyl (acrylate) (ASMA) monomer or its salt of at least one amino substitution；(b) it is at least one Non-ionic vinyl (NIV) monomer of kind；(c) it is at least one vinyl association (VA) monomer；(d) it is at least one vinyl Surfactant (VS) monomer；(e) it is at least one polymerizable silicone macromonomer (PSM)；It is above-mentioned with any of which Mixture optionally further contains：(f) at least one crosslinking (XL) monomer；(g) at least one chain-transferring agent (CTA)；(h) extremely A kind of few polymer stabilizer；Or component (f), (g) and/or (h) in any suitable combination of two or more, wherein should Monomer mixture includes, with the total weight of monomer mixture, the component (a) of about 1wt%- about 90wt%；About 20wt%- about 80wt% Component (b)；The component (c) of about 0.01wt%- about 25wt%；The component (d) of about 0.01wt%- about 25wt%；About 0.01wt%- is about The component (e) of 10wt%；The most about component (f) of 5wt%；The most about component (g) of 10wt%；The most about component of 2wt% (h)。
In still another embodiment, the present invention relates to the polymer of hydrolysis-stable, mixed for the monomer comprising following monomer Close the reaction product of the polymerization of object：
(i) (a), (b) and (c)；
(ii) (a), (b) and (d)；
(iii) (a), (b) and (e)；
(iv) (a), (b), (c) and (d)；
(v) (a), (b), (c) and (e)；
(vi) (a), (b), (d) and (e)；Or
(vii) (a), (b), (c), (d) and (e),
Wherein (a) is methyl (acrylate) (ASMA) monomer or its salt of at least one amino substitution；(b) it is at least one Non-ionic vinyl (NIV) monomer of kind；(c) it is at least one vinyl association (VA) monomer；(d) it is at least one vinyl Surfactant (VS) monomer；(e) it is at least one polymerizable silicone macromonomer (PSM)；It is above-mentioned with any of which Mixture optionally further contains：(f) at least one crosslinking (XL) monomer, (g) at least one chain-transferring agent (CTA), (h) extremely A kind of few polymer stabilizer or component (f), (g) and/or (h) in any suitable combination of two or more, wherein should Monomer mixture includes, with the total weight of monomer mixture, the component (a) of about 10wt%- about 80wt%；About 20wt%- is about The component (b) of 70wt%；The component (c) of about 0.1wt%- about 15wt%；The component (d) of about 0.1wt%- about 10wt%；About 0.1wt%- The component (e) of about 7.5wt%；The about 0.01 most about component (f) of 5wt%；The component (g) of about 0.1- about 10wt%；About with 0.001- The component (h) of 2wt%.
Description of the drawings
Fig. 1 is the mapping of the acid values of various monomers to the time when being placed under hydrolysising condition；
Fig. 2 is to pass through1Work of the percent hydrolysis of DMAEMA and DMADMPMA that H NMR are measured at 500Hz to the time Figure；
Fig. 3 be examples of polymer 1 (DMAPMA) and examples of polymer 2 (DMAPMA/DMADMPMA) acid value to latex 45 DEG C storage all numbers mapping；
Fig. 4 is the 2%TS viscosity of embodiment 1 (DMAPMA) and examples of polymer 2 (DMAPMA/DMADMPMA) to latex 45 DEG C storage all numbers mapping；
Fig. 5 be based on commercial polymers DMAEMA (reference material 3, INCI:Polyacrylate -1Crosspolymer), it is poly- The work for all numbers that conjunction object example 4 (DMADMPMA) and the acid value of examples of polymer 7 (DMADMPMA) store latex at 50 DEG C Figure；
Fig. 6 be based on commercial polymers DMAEMA (reference material 3, INCI:Polyacrylate -1Crosspolymer), it is poly- What conjunction object example 4 (DMADMPMA) and the 2%TS gel viscosities of examples of polymer 7 (DMADMPMA) stored latex at 50 DEG C The mapping of all numbers；
Fig. 7 be based on commercial polymers DMAEMA (reference material 3, INCI:Polyacrylate -1Crosspolymer), it is poly- The acid value of conjunction object example 1, examples of polymer 2, examples of polymer 4, examples of polymer 6, examples of polymer 7 and examples of polymer 9 To latex the months of room temperature storage mapping；With
Fig. 8 be based on commercial polymers DMAEMA (reference material 3, INCI:Polyacrylate -1Crosspolymer), it is poly- 2% gel viscosity of object example 4, examples of polymer 6, examples of polymer 7 and examples of polymer 9 is closed to latex in room temperature storage Months mapping.
Detailed description of the invention
It is the polymerizate for including monomer mixture below the present invention relates to multi-purpose polymer：At least one ammonia Methyl (acrylate) (ASMA) monomer or its salt and at least one non-ionic vinyl (NIV) monomer of base substitution, wherein The monomer mixture further includes at least one vinyl association (VA) monomer, at least one vinyl surfactant (VS) It is one or more in monomer, and/or at least one polymerizable silicone macromonomer (PSM), and wherein the monomer is mixed Conjunction object includes optionally further at least one crosslinking (XL) monomer, at least one chain-transferring agent (CTA), and/or at least one It is one or more in polymer stabilizer.The multi-purpose polymer of the present invention can also be by containing chain-transferring agent or in polymerization technique It is prepared by the monomer mixture of common other function ingredients.In one embodiment, multi-purpose polymer of the invention is long Time (for example, more than 6 months or longer period) hydrolysis-stable, it is provided in acidic aqueous compositions wondrous Beneficial rheologic behavio(u)r, and it is compatible with cationic materials.The multi-purpose polymer of the present invention can be used for various products, wrap It includes but is not limited to, personal care product, health care products, household care products, public organizations and industrial nursing product and work In industry application.
The present invention polymer be typically alkalinity, it is insoluble, swellable in aqueous acids or in aqueous acids it is soluble Polymer and its salt contain the amino-substituent at least one alkalinity for being at a low ph cation and derived from vinyl association (VA) polyoxyalkylene substituent of at least one hydrophobically modified of monomer, and optionally contain and derive from vinyl surfactant (VS) at least one polyoxyalkylene substituent of monomer.In addition, the polymer of the present invention also optionally contains derived from other Nonionic vinyl monomer unit, chain-transferring agent unit and the polymer of monomeric unit such as cross-linking monomer unit, hydroxyl substitution The substituent group of stabilizer etc..The polymer of the present invention usually shows associative property in aqueous solution.For convenience's sake, this hair Bright polymer is commonly referred to as " multi-purpose polymer " herein.Term " low ph formulations " refers to being arrived about 0.5 with range Arrive no more than about 7 or even the preparation for the acid pH for being not greater than about 6.5.
Term as used herein " (methyl) acrylic acid " refer to include acrylic acid and methacrylic acid.Similarly, herein Used term " (methyl) acrylate " refer to include acrylate and methacrylate.Term " (methyl) acryloyl Amine " is for including both acrylamide and Methacrylamide.
Term " aqueous (aqueous) " for preparation or medium refers to water to be enough at least multi-purpose polymer to be made to be swollen Or it includes that amount in composition in it exists to be dissolved in it.
It has now been found, surprisingly, that the multi-purpose polymer of the present invention provides improved preservation in about 6 months or longer Phase.In addition, aqueous personal nursing, health care, residential care and industrial and machine that the multi-purpose polymer of the present invention is low pH Structure care product provides required rheologic behavio(u)r.The multi-purpose polymer of the present invention is cationic-compatible, this makes them Especially it can be used as thickener in the product containing quaternary ammonium salt or amine.It is surprising that the multi-purpose polymer of the present invention Can be used for containing one or more of surfactants (for example, anion, it is cationic, both sexes, non-ionic, and/or With the combination of these any two or more) composition in, and also provide hair fixing effect.The multipurpose of the present invention Polymer is useful thickener in the product containing active acid constituent, and is for the useful of lotion (creams, washing lotion) Thickener and emulsifier.Other than thickening, multi-purpose polymer of the invention is useful film forming agent, sprawls auxiliary agent and heavy Product auxiliary agent, for containing surfactant, colorant, hair and skin-care agent, type siloxane, poly quaternary ammonium compound, anti-head Consider agent, age resister, anti-cellulite agent, anti-acne agents, vitamin, analgesic, anti-inflammatory compound, self-tanning agent, natural on-off cycles of hair growth to be worth doing Accelerating agent, UV protective agents, skin-whitening agents, vegetables, plant, the extract of botanical, antiperspirant, antioxidant, taste removal The product of polymer, soothing oil and combinations thereof is determined in agent, hair.
Term as used herein " personal care product " includes but not limited to the skin for being applied to human and animal, hair Hair, scalp and cosmetics on nail, cosmetics, medicine adornment (cosmeceuticals) and beauty aids, personal hygiene and cleaning Product.Term as used herein " health care products " includes but not limited to drug, medicine adornment, oral care product (oral cavity, tooth Tooth), eyeware products and solution for lenses and contact lenses, ear's care product and over-the-counter products and apparatus, such as patch, plaster, dressing etc., and it is outer Portion be administered to the medical apparatus on the body of human and animal or in body to mitigate with related or medicine the situation of health, To generally maintain health or good state etc..Term " body " include entire body (face, trunk, four limbs, head and Foot) cuticula (hair, nail) and non-keratinocyte layer skin area, body key and eye tissue, and term " skin " includes Scalp and mucous membrane.It is for example that term as used herein " household care products " including but not limited to uses in daily life Sanitary condition is kept in kitchen and bathroom and is used for surface cleaning or the cleaning products of biocidal, and for fabric nursing and clearly Clean cleaning product etc..Term as used herein " public organizations and industrial nursing " and " I＆I " include but not limited in industry With in public organizations' environment, including hospital and health care facilities for cleaning or maintain product used in sanitary condition etc..
The multi-purpose polymer of the present invention is the polymer of hydrolysis-stable, in one embodiment, is contained by polymerization It is prepared by the mixture of following monomers：
(i) (a), (b) and (c)；
(ii) (a), (b) and (d)；
(iii) (a), (b) and (e)；
(iv) (a), (b), (c) and (d)；
(v) (a), (b), (c) and (e)；
(vi) (a), (b), (d) and (e)；Or
(vii) (a), (b), (c), (d) and (e),
Wherein (a) is methyl (acrylate) (ASMA) monomer or its salt of at least one amino substitution；(b) it is at least one Non-ionic vinyl (NIV) monomer of kind；(c) it is at least one vinyl association (VA) monomer；(d) it is at least one vinyl Surfactant (VS) monomer；(e) it is at least one polymerizable silicone macromonomer (PSM)；It is above-mentioned with any of which Mixture optionally further contains：(f) at least one crosslinking (XL) monomer；(g) at least one chain-transferring agent (CTA)；(h) extremely A kind of few polymer stabilizer；Or component (f), (g) and/or (h) in any suitable combination of two or more.The present invention Multi-purpose polymer can also be by the monomer mixture system of common other functional monomers containing chain-transferring agent or in polymerization technique It is standby.
In one embodiment, the multi-purpose polymer of hydrolysis-stable of the invention is comprising monomer mixture below Polymerizate：With at least one ASMA monomers or its salt of the total weight (a) of monomer mixture about 10wt%- about 90wt%； (b) at least one NIV monomers of about 20wt%- about 80wt%；(c) at least one VA monomers of about 0.01wt%- about 25wt%；(d) At least one VS monomers of most about 25wt%；(e) at least one polymerizable silicone of about 0.01wt%- about 10wt% divides greatly Sub- monomer (PSM)；(f) the XL monomers of most about 5wt%；(g) the most about CTA of 10wt%；(h) the most about polymer of 2wt% Stabilizer.
In another embodiment, multi-purpose polymer of the invention is that the polymerization comprising monomer mixture below is produced Object：With at least one ASMA monomers or its salt of the total weight (a) of monomer mixture about 10wt%- about 80wt%;(b) about At least one NIV monomers of 20wt%- about 70wt%;(c) at least one V monomers of about 0.1wt%- about 15wt%;(d) about At least one VS monomers of 0.1wt%- about 10wt%;(e) at least one polymerizable silicone of about 0.1wt%- about 7.5wt% is big Molecule monomer (PSM)；(f) the XL monomers of about 0.001wt%- about 5wt%;(g) CTA of about 0.1wt%- about 5wt%.Herein and In the other places of description and claims, in combination with individual numerical value or bound, formed additional undisclosed and/or not described And range.
In yet another embodiment, multi-purpose polymer of the invention is that the polymerization comprising monomer mixture below is produced Object：Free style (I), I (a) and/or (II) is selected to indicate with the total weight (a) of monomer mixture about 20wt%- about 70wt% Methyl (acrylate) (ASMA) monomer of at least one of one or more monomers amino substitution：
Wherein R1、R2、R3And R4Defined below and CA-The charge being suitable on balance quaternary ammonium group contend with it is cloudy from Son；(b) about 50wt%- about 65wt% be selected from acrylic acid C1-C30Arrcostab, methacrylic acid C1-C30Arrcostab or they in At least one of any suitable mixture of two or more nonionic ethylene base (NIV) monomer；(c) about 0.1wt%- About 10wt%'s is selected from cetyl polyethoxylated methacrylate ester (CEM), cetearyl polyethoxylated methacrylate Ester (CSEM), stearyl polyethoxylated (methyl) acrylate, eicosyl polyethoxylated (methyl) acrylate, 20 Dialkyl group polyethoxylated methacrylate ester (BEM), lauryl polyethoxylated methacrylate ester (LEM), hexacosane Base polyethoxylated (methyl) acrylate, octacosyl polyethoxylated (methyl) acrylate, the poly- ethoxy of melissyl Base (methyl) acrylate, dotriacontyl polyethoxylated (methyl) acrylate, triphenyl vinyl phenol polyethoxy Change methacrylate (TEM), rilanit special polyethoxylated methacrylate ester (HCOEM), rapeseed oil polyethoxylated At least one of (methyl) acrylate and cholesterol polyethoxylated methacrylate ester (CHEM) vinyl associate (VA) Monomer；(d) at least one vinyl surfactant (VS) monomer indicated by formula (VI) of about 0.1wt%- about 10wt%：
Wherein each R6It independently is hydrogen or methyl ,-C (O) OH or-C (O) OR7;R7It is C1-C30Alkyl；A is-CH2C(O) O- ,-C (O) O- ,-O- or-CH2O-；It is 0 or 1 that p, which is range in the integer and r of 0- about 30, and condition is that r is 0 when p is 0, and When the range of p is in about 30 1-, r is 1；(R8-O)vIt is polyoxy alkylidene, is C2-C4The homopolymer of oxygroup alkylidene unit, nothing Copolymer or block copolymer are advised, wherein each R8It independently is C2H4、C3H6、C4H8Or they mixing and v be range about The integer of 1- about 250 either about 5- about 100 or about 10- about 80 or even about 15- about 60；And R9It is hydrogen or C1-C4Alkyl； (e) at least one polymerizable silicone macromonomer (PSM) of about 1wt%- about 7.5wt%；(f) the most about crosslinking of 5wt% (XL) monomer;(g) the most about chain-transferring agent of 10wt% (CTA)；(h) the most about polymer stabilizer of 2wt%.Herein and In the other places of description and claims, individual numerical value or bound from each independent embodiment can be combined, Form the additional range being not disclosed and/or do not address.
Term used herein " alkyl " refers to substituted or unsubstituted aliphatic hydrocarbon group, including straight chain, it is branched With the alkyl group point of carbocyclic ring.Term " carbocyclic ring alkyl " refers to containing the carbocyclic ring that one or more sizes are about 12 carbon atoms of 3- Ring and optionally include the alkyl of alkyl substituent on the ring of carbocyclic ring.Term " aryl " includes substitution and unsubstituted phenyl And naphthyl group.“Cx-Cy" the modification mode of form indicates that alkyl or carbocyclic ring alkyl have containing the molecule for amounting to x-y carbon atom Formula, wherein x and y are defined integers.Term " mixed ester (complex used in herein and in the following claims Ester) " refer to polyalcohol, such as with C can be used2-C7Two, the three or more of the sugar of the alkylated at least one hydroxyl of alkylene oxide Ester.In a kind of situation, term " mixed ester " is included in the mixing hydrophobe described in United States Patent (USP) No.5639841, the patent Relevant disclosure be incorporated by reference herein.
The term " halogen substitution " that uses here in connection with alkyl or aryl etc., " hydroxyl substitution ", " carboxyl substitution ", " polyoxy alkylidene substitution ", " alkyl-substituted " and " aryl substitution " refers at least one on the groups such as alkyl, aryl A hydrogen atom is substituted by least one halogen atom, hydroxyl, carboxyl, polyoxy alkylidene, alkyl or aryl respectively.In the side of replacement In case, term used herein " poly- (methyl) acrylate " and " poly- (methyl) acrylamide " refer respectively to polyacrylate Or polymethacrylates and polyacrylamide or polymethacrylamide.
The suitable monomer that can be used for preparing the multi-purpose polymer of the present invention is as described below.It is mixed about monomer, monomer Object and be used to form multi-purpose polymer of the present invention " charging (charge) " each component amount, it shall be noted that it is following.Although When being taken separated from simultaneously adduction with widest dosage disclosed herein, the total amount of each monomer or component can be independent in various " chargings " Ground totals over 100wt%, but those skilled in the art can be appreciated that situation is not in this way.On the contrary, the present invention respectively reacts Each individual component in " charging " (i.e. component (a) arrives (e), including component (a) and (e), and if existing component (f) and (g)) What can change in the range optionally in office, to realize the total weight of 100wt%.
ASMA monomers：
Being suitable for methyl (acrylate) (ASMA) monomer of the amino substitution of the multi-purpose polymer of the preparation present invention is Alkaline, polymerizable ethylenically unsaturated monomers containing at least one amido functional group.These basic amine groups, which can derive from, to be contained Mono-, di- or polyamino alkyl or nitrogen heteroaryl.Amino may include primary, secondary or tertiary amine.Monomer can be optionally with amine-format Or salt form uses.
In one embodiment, polymer of the invention includes being selected to be indicated by formula (I) and (I I) as follows One or more of ASMA monomers in monomer：
Wherein R1It is methyl；Wherein R2It is substituted or unsubstituted, straight chain or branched C2-C8Alkane diyl (has at least The alkyl of two free chemical valences), condition is to work as R2There are two R when carbon for tool2In base two carbon atoms it is at least one by straight chain or Branched C1-C30Alkyl substitution (for example, monosubstituted or two substitutions)；Wherein each R3Independently selected from hydrogen, straight chain or branched C1- C30Alkyl contains one or more heteroatomic straight chains or branched C1-C30Alkyl, straight chain or branched C2-C30Alkenyl contains One or more heteroatomic straight chains or branched C2-C30Alkenyl, straight chain or branched C2-C30Alkynyl contains one or more Heteroatomic straight chain or branched C2-C30Alkynyl, C4-C20Aryl contains one or more heteroatomic C4-C20Aryl, C4-C20 Naphthenic base contains one or more heteroatomic C4-C20Naphthenic base, C4-C20Heterocycle or in which two R3Substituent group and they The nitrogen-atoms being connected thereto can form saturated or unsaturated C2-C20Heterocycle has two or more hetero atoms Saturated or unsaturated C2-C20Heterocycle, wherein hetero atom in the presence of selected from carbonyl, N, S, P or O；R4It is straight chain or branch The C of change1-C30Alkyl；Wherein CA-It is suitable for the counter anion of the charge on balance quaternary ammonium group.In another embodiment party In case, R1It is methyl；Wherein R2It is substituted or unsubstituted, straight chain or branched C3-C7Alkane diyl (has at least two trips Alkyl from chemical valence), wherein each R3Independently selected from hydrogen, straight chain or branched C3-C15Alkyl contains one or more miscellaneous originals The straight chain or branched C of son3-C15Alkyl, straight chain or branched C4-C20Alkenyl, containing one or more heteroatomic straight chains or Branched C4-C20Alkenyl, straight chain or branched C4-C20Alkynyl contains one or more heteroatomic straight chains or branched C4-C20 Alkynyl, C5-C10Aryl contains one or more heteroatomic C5-C10Aryl, C5-C10Naphthenic base contains one or more miscellaneous originals The C of son5-C10Naphthenic base, C5-C10Heterocycle or in which two R3Substituent group and the nitrogen-atoms that they are connected thereto can be with shapes At saturated or unsaturated C3-C10Heterocycle has two or more heteroatomic saturated or unsaturated C3-C10It is miscellaneous Ring group, wherein hetero atom in the presence of selected from carbonyl, N, S, P or O；R4It is straight chain or branched C2-C20Alkyl；Wherein CA-It is It is suitable for balancing the counter anion of the charge on quaternary ammonium group.It, can herein and in the other places of description and claims Individual numerical value (including carbon atom number value) or bound are combined, the additional model being not disclosed and/or do not address is formed It encloses.
In yet another embodiment, R1It is methyl；R2It is substituted or unsubstituted, straight chain or branched C4-C6Alkane diyl (i.e. the alkyl at least two free chemical valences), each R3Independently selected from hydrogen, straight chain or branched C5-C8Alkyl contains one A or multiple heteroatomic C5-C8Alkyl, straight chain or branched C6-C10Alkenyl contains one or more heteroatomic straight chains or branch The C of change6-C10Alkenyl, straight chain or branched C6-C10Alkynyl contains one or more heteroatomic straight chains or branched C6-C10Alkynes Base, C5-C8Aryl contains one or more heteroatomic C5-C8Aryl, C5-C8Naphthenic base, containing one or more heteroatomic C5-C8Naphthenic base, C5-C8Heterocycle or in which two R3Substituent group and the nitrogen-atoms that they are connected thereto can form saturation Or undersaturated C4-C8Heterocycle has two or more heteroatomic saturated or unsaturated C4-C8Heterocycle, Middle hetero atom in the presence of selected from carbonyl, N, S, P or O；Wherein R4It is straight chain or branched C3-C15Alkyl；Wherein CA-It is It is suitable for balancing the counter anion of the charge on quaternary ammonium group.It, can herein and in the other places of description and claims Individual numerical value (including carbon atom number value) or bound are combined, formed additional undisclosed and/or is not addressed Range.
About the compound of formula (II), these compounds are the corresponding quaternary ammonium compounds of the compound indicated by formula (I). It will be obvious to a person skilled in the art that the monomeric compound of formula (II) passes through the compound that makes to be indicated by formula (I) With formula CA-R4Alkyl halide compounds carry out quaternary reaction generation, wherein R4It is straight chain defined above or branched alkane Base, and wherein CA are that any of counter anion is generated when reaction forms the quaternary ammonium compound of the compound indicated by formula (II) Suitable substance and/or group point.In one embodiment, CA and/or CA-Suitable substance and/or group include, but It is not limited to, halogen (for example, bromine, chlorine, fluorine or iodine), sulfate radical, sulfonate radical, phosphate radical and phosphonate radical.In another embodiment In, the suitable substance and/or group of CA and/or CA- include, but are not limited to chlorion, bromide ion, methyl-sulfuric acid root (that is, first Base sulfate radical), acetate, formate, sulfate radical, nitrate anion etc..In still another embodiment, CA and/or CA-It is halogen, example Such as chlorine, bromine or fluorine.
In still another embodiment, the monomer of formula (I) can be with hydrogen peroxide (H2O2) reaction, generate the amine being expressed from the next Oxide compound：
Wherein R1、R2And R3As defined above.In addition, be made the present invention multi-purpose polymer after, can carry out more than Refer to slave formula (I) to formula (II) or any one of the conversion process of above-mentioned amine oxide.
In another embodiment, the charging of ASMA monomers is the mixture of the compound according to formula (I) and (II).One In kind of situation, according to the monomer of formula (I) with according to the weight ratio range of the amount of the quaternary monomer of formula (II) about 5:95- about 95: 5, or about 10:90-90:10, or about 15:85-85:15, or about 20:80- about 80:20, or about 25:75- about 75:25, or about 30: 70-70:30, or about 35:65-65:35, or about 40:60- about 60:40, or about 45:55- about 55:45, or even about 50:50.This Place and in the other places of description and claims, can combine individual numerical value or bound, form additional be not disclosed And/or the range that do not address.
Term " alkane diyl " used in the whole instruction and claim is defined as referring to having at least two trips Alkyl from chemical valence.Free chemical valence can be located at the terminal sites and/or any in the group skeleton on the group On carbon atom.For illustrative purposes, straight chain and the non-limiting example of branched alkane diyl part have (only with single carbon atom phase Line even indicates the chemical valence that dissociates)：
The example of specific ASMA monomers includes, but are not limited to those shown below：
Methacrylic acid 4- (dimethylamino) butyl ester
Wherein it can indicate above compound with following abbreviations：Methacrylic acid 3- (dimethylamino) propyl ester (DMAPMA)； Methacrylic acid 1- (dimethylamino) propyl- 2- base esters (DMAIPMA)；Methacrylic acid 3- (dimethylamino) -2,2- diformazans Base propyl ester (DMADMPMA)；Methacrylic acid 2- (dimethylamino) -2- methyl propyl ester (DMAMPMA)；With methacrylic acid 4- (dimethylamino) butyl ester (DMABMA).
The suitable salt form of above-mentioned monomer includes, but are not limited to inorganic hydrochloric acid, such as hydrochloride, sulfate and phosphoric acid Salt；And acylate, such as acetate, citrate, glycollate, lactate, maleate and fumarate etc..
Aforementioned monomer or its salt can be used as multi-purpose polymer of the present invention individually or with the mixture of two or more Amino substitution vinyl monomer components.
In one embodiment, ASMA monomers account for about 5wt%- about 90wt%, or about 10wt%- about 80wt%, or about 15wt%- about 70wt%, or about 20wt%- about 60wt%, or about 25wt%- about 50wt%, or even about 30wt%- about 40wt%, are based on The total weight of monomer mixture.Herein and in the other places of description and claims, individual numerical value can be combined (wherein Including carbon atom number value) or bound, form the additional range being not disclosed and/or do not address.
Due to the use of the ASMA monomers in formula (I) illustrated above, I (a) and/or (II), therefore the present invention's is poly- Object is closed to be used to produce the multipurpose copolymer with improved storage life using the amine monomers of one or more of hydrolysis-stables.Such as Upper described, the storage life of multipurpose copolymer of the invention is at least about 6 months, at least about 9 months, at least about 12 months, until Few about 18 months or storage life even at least about 24 months or longer.Herein and in the other places of description and claims In, individual numerical value (including carbon atom number value) or bound can be combined, is formed additional undisclosed and/or not described And range.
" storage life " though refer to the multipurpose copolymer of the present invention in aqueous solution or under environment when still keep stablizing and Not because excessive degradation occurs for hydrolysis discussed above.
Although being not intended to be bound by any type theory, even if it is believed that the multipurpose copolymer of the present invention in aqueous solution Or when under environment still keep stablize and not because hydrolysis discussed above occur excessive degradation be due to many factors, including But it is not limited to, extended chain length is (straight chain and branched between one or more amino functionalities and acrylate functionalities ).In still another embodiment, it was surprisingly found now that can be by being used containing branched R according to embodiments described above2 And/or extended R2Base can mitigate and/or eliminate the multipurpose polymerization formed in various embodiments according to the present invention Hydrolysis in the ester moiety of the amino ester moiety of object.It is believed that it reduce formed in hydrolysis in 5 membered rings described in detail above The tendency of mesosome.Meanwhile such method also increases the hydrophobicity of monomer and reduces its dissolubility in water.It is wondrous Ground, the combination of both methods (chain length and hydrophobicity that increase ASMA monomer molecules), which is provided, to be formed according to the present invention by it The unexpected stability of multipurpose copolymer.In addition, in the multipurpose copolymer formed by it according to the present invention, lead to It crosses with the straight chain or the internal hydrogen atom of branched alkyl substitution above in relation to formula (I) and (II) discussion, " guarantor of end-vinyl ester group Shield " additionally provides improved and unexpected stability.
The ASMA monomers of the present invention can be used for mitigating the weight containing by dimethylaminoethyl acrylate methyl base ammonia ethyl ester (DMAEMA) being polymerize Intrinsic hydrolytic instability in the polymer of multiple unit.The ASMA monomers of the present invention can be added to gathering for the monomer containing DMAEMA It closes in monomer mixture, to mitigate the hydrolytic instability of the polymer containing the repetitive unit derived from DMAEMA.The present invention's In one side, it may include the amount ranges of the ASMA monomers in the monomer mixture containing polymerizable DMAEMA from about 1-99 The ASMA monomers of parts by weight are based on 100 parts by weight ASMA monomers and DMAEMA monomers to the DMAEMA monomers of about 99-1 parts by weight Total weight.In another aspect, monomer mixture contains the ASMA monomers and about 90-10 parts by weight of about 10-90 parts by weight DMAEMA monomers.In another aspect, monomer mixture contains the ASMA monomers and about 80-20 weight of about 20-80 parts by weight Part DMAEMA monomers.In another further aspect, monomer mixture contains the ASMA monomers and about 70-30 weight of about 30-70 parts by weight The DMAEMA monomers of part.In further aspect, monomer mixture contains the ASMA monomer peace treaties of about 40-60 parts by weight The DMAEMA monomers of 60-40 parts by weight.Further aspect in, monomer mixture contain about 50 parts by weight ASMA monomers and About 50 parts by weight DMAEMA monomers.Total weight of ASMA monomer and DMAEMA monomer of all in terms of foregoing based on 100 parts by weight Amount.Other polymerisable monomers can be added in polymerizable monomer mixture, such as above-described NIV, V, VS, PSM and XL mono- It is one or more in body.
The tendentious suitable ASMA monomers of unfavorable hydrolysis that can be used for mitigating the polymer derived from DMAEMA include meeting One or more ASMA monomers of above-described Formulas I, I (a) and II.Representative ASMA monomers are selected from methacrylic acid 3- (two Methylamino) propyl ester (DMAPMA)；Methacrylic acid 2- (dimethylamino) propyl- 2- base esters (DMAIPMA)；Methacrylic acid 3- (dimethylamino) -2,2- dimethyl propyl ester (DMADMPMA)；Methacrylic acid 2- (dimethylamino) -2- methyl propyl ester (DMAMPMA)；With methacrylic acid 4- (dimethylamino) butyl ester (DMABMA).It can dosage and range use symbol listed above The monomer and specific representative monomers disclosed herein of box-like I, I (a) and II.
Nonionic ethylene base (NIV) monomer for being suitable for using in the multi-purpose polymer for preparing the present invention is by formula (III) and/or (IV) indicate copolymerizable non-ionic ethylenically unsaturated monomers：
C(X)2=C(X)Z (III)
CH2=CH-OC(O)R1 (IV)
Wherein in each formula (III) and (IV), each X independently is hydrogen, methyl ,-CH2C(O)OR1、-C(O)OR1；With Z be- C(O)OR1、-C6H4R1、-C6H4OR1、-CN、-C(O)N(R1)2、-NHC(O)CH3、-NHC(O)H、-C(O)OA'OR15, N- (2- pyrroles Pyrrolidone base), N- caprolactams base ,-C (O) NHCH2CH2- N- ethylidene-ureas or-C (O) NHC (CH3)3；A' is to be selected from-CH2CH (OH)CH2And-CH2CH(CH2OH)-bivalent group, each R1It independently is straight chain and branched C1-C30Alkyl, hydroxyl substitution C2-C30Alkyl, C5-C30Naphthenic base and C1-C5Alkyl-substituted C5-C30Naphthenic base；R15Be straight chain or it is branched, saturation or not It is saturated C6-C22The acyl residue of aliphatic acid.
The non-limiting example of suitable nonionic vinyl monomer includes (methyl) acrylic acid C1-C30Arrcostab；C1-C30 Alkyl (methyl) acrylamide；Styrene；Substituted phenylethylene, such as vinyltoluene, (for example, 2-methyl styrene), butyl Styrene, isopropyl styrene etc.；Vinyl esters, such as vinyl acetate, vinyl butyrate, new vinyl acetate acid, caproic acid second Enester, vinyl caproate (vinyl caprolate), vinyl pelargonate ester, caprate, vinyl neodecanoate, hendecanoic acid Vinyl acetate, vinyl laurate etc.；Unsaturated nitrile, such as methacrylonitrile, acrylonitrile, and can be with trade name ACETM(M) ACETMMonomer is obtained from the monomer of Hexion Specialty Chemicals, Inc., Columbus, OH..
ACE monomers (CAS No.94624-09-06) are tertiary capric acid ethylene oxidic ester (CASNo.71206-09-2) and propylene The reaction product of acid.(M) ACE monomers are synthesized by so that tertiary capric acid ethylene oxidic ester and methacrylic acid is reacted.Pass through shrink Glycerine and C6-C22Fatty acid response obtains the ethylene oxidic ester of each aliphatic acid via esterification, can synthesize according to formula (III) Wherein Z is-C (O) OA'OR15Other monomers.The ethylene oxidic ester being thusly-formed both and can by its epoxy functional degree with Carboxylic group reaction in (methyl) acrylic acid, obtains preformed monomer.
In one aspect of the invention, form above-described preformed monomer component (ACE and (M) ACE)) conjunction Suitable ethylene oxidic ester is disclosed in United States Patent (USP) No.5, and in 179,157 (the 13rd columns), relevant disclosure is herein by drawing With being included in.The ethylene oxidic ester of neodecanoic acid and its isomers is with trade name CarduraTME10P is available commercially from Hexion Specialty Chemicals,Inc.。
In another embodiment, nonionic ethylene base (NIV) monomer includes the C of acrylic acid and methacrylic acid1-C30Alkane Base ester and its mixture, such as methyl acrylate (MA), ethyl acrylate (EA), methyl methacrylate (MMA), acrylic acid are just Butyl ester (nBA), 2-EHA (2-EHA), methacrylic acid 3,3,5- 3-methyl cyclohexanols ester (TMCHMA), methyl-prop Olefin(e) acid stearyl ester (SMA) and in them any two or more suitable mixture.
In still another embodiment, nonionic ethylene base (NIV) monomer being employed in conjunction with the invention includes, but unlimited In the C of acrylic acid and methacrylic acid1-C30The hydroxyl C of Arrcostab, acrylic acid and methacrylic acid2-C30Arrcostab and they The mixture of middle any two or more.The example include, but are not limited to methyl acrylate (MA), ethyl acrylate (EA), Methyl methacrylate (MMA), n-butyl acrylate (nBA), 2-EHA (2EHA) and methacrylic acid are stearic Ester (SMA)；Unsaturated dicarboxylic C1-C30Dialkyl ester such as diethyl itaconate；Vinyl acetate such as vinyl neodecanoate, n-nonanoic acid Vinyl acetate and hendecanoic acid vinyl acetate；N-vinyl pyrrolidone；C1-C30Alkyl (methyl) acrylic amine, such as metering system Amide and t-butylmethacrylamide；Styrene；Carbocyclic ring C1-C30Alkyl-substituted methyl acrylic ester, such as methyl-prop Olefin(e) acid cyclohexyl and 3,3,5- 3-methyl cyclohexanol ester (TMCHMA) of methacrylic acid and any two or more in them Suitable mixture.
In one embodiment, NIV monomers account for about 0.01wt%- about 90wt%, or about 0.1wt%- about 85wt%, or about 1wt%- about 80wt%, or about 5wt%- about 75wt%, or about 10wt%- about 70wt%, or about 15wt%- about 65wt%, or about 20wt%- About 60wt%, or about 25wt%- about 55wt%, or about 30wt%- about 50wt%, or even about 35wt%- about 45wt%, it is mixed based on monomer Close the total weight of object.Herein and in the other places of description and claims, individual numerical value can be combined (including carbon Atom numerical value) or bound, form the additional range being not disclosed and/or do not address.
In still another embodiment, multi-purpose polymer of the invention can be prepared by the monomer mixture of the monomer containing NIV, The NIV monomers are the ethylenically unsaturated monomers containing one or more hydroxyl substituents.The reality of this kind of suitable NIV monomers Example includes, but are not limited to the (C of the hydroxyl substitution of (methyl) acrylic acid1-C4) Arrcostab, such as 2-Hydroxyethyl methacrylate (HEMA), acrylic acid 2- hydroxyl ethyl esters (2-HEA), acrylic acid 3- hydroxypropyl acrylates etc.；(the C of hydroxyl substitution1-C4) alkyl (methyl) propylene Amide, for example, N- (2- ethoxys) Methacrylamide, N- (2- ethoxys) acrylamide, N- (3- hydroxypropyls) acrylamide, N- (2,3- dihydroxypropyls) acrylamide etc..Other useful NIV monomers include allyl alcohol, allylin, 3- Methyl-3-butene-1-alcohol and vinyl alcohol precursor and equivalent, such as vinyl acetate.
In one embodiment, monomer reaction mixture of the invention contains one or more in one embodiment Any NIV monomers disclosed above, in an amount of from the most about 15wt% based on monomer mixture total weight.In another embodiment party In case, the range of the amount of NIV monomers is in about 0.01wt%- about 15wt%, or about 0.1wt%- about 10wt% in the mixture, or about 1wt%- about 8wt%, or even about 1wt%- about 5wt%, the total weight based on monomer mixture.Herein and in specification and power In the other places that profit requires, individual numerical value (including carbon atom number value) or bound can be combined, forms additional not public affairs The range opened and/or do not addressed.
VA monomers：
In one embodiment, it is single to be suitable for the vinyl used in the multi-purpose polymer of the production present invention association Body (VA) is that have compound below：(A) it is used for the ethylenic bond unsaturation terminal portion with other monomer addition polymerizations in system； (B) it is used to assign the polyoxy alkylidene middle section of resulting polymer selectivity hydrophilicity；(C) for polymer for providing The hydrophobic terminal portion of selective hydrophobic performance.
In one embodiment, the part (A) for providing ethylenic bond unsaturation end group derives from α, and β-ethylenic bond is unsaturated single Or dicarboxylic acids or their acid anhydrides, or even C3Or C4List or dicarboxylic acids or their acid anhydrides.Alternatively, vinyl association (VA) is single (A) in body can partly derive from allyl ether or vinyl ethers；The carbamate monomer of non-ionic vinyl substitution, example As disclosed in U.S. Reissue No.33,156 or United States Patent (USP) No.5,294,692 those；Or the urea of vinyl substitution Reaction product, such as United States Patent (USP) No.5, disclosed in 011,978 those；The relevant disclosure of above-mentioned document passes through herein Reference is included in.
In one embodiment, middle section (B) is about 5- about 250, or about 10- about 120, or even about 15- About 60 repetition C2-C7The polyoxy alkylidene segment of oxygen alkylidene unit.In one embodiment, middle section (B) includes Containing about 5- about 150 or about 10- about 100 or even about 15- about 60 ethylene oxide, propylene oxide or epoxybutane units With random or non-random sequence the polyethylene oxide of ethylene oxide, propylene oxide or epoxybutane unit, polypropylene oxide and Polybutylene oxide segment.Herein and in the other places of description and claims, individual numerical value can be combined (including carbon Atom numerical value) or bound, form the additional range being not disclosed and/or do not address.
In one embodiment, the hydrophobic terminal portion (C) in vinyl association (VA) monomer is to belong to following hydro carbons One of other hydrocarbyl group：C8-C40The C that straight chained alkyl, aryl replace2-C40Alkyl, C2-C40Alkyl-substituted phenyl, C8-C40Branch Alkyl, the C of change8-C40Carbocyclic ring alkyl；And C8-C80Mixed ester.
The non-limiting example of suitable hydrophobic terminal portion (C) in vinyl association (VA) monomer has with about 8- about The straight chain or branched alkyl of 40 carbon atoms, such as octyl (C8), iso-octyl (branched C8), decyl (C10), lauryl (C12)、 Myristyl (C14), cetyl (C16), cetearyl (cetearyl, C16-C18), stearyl (C18), iso stearyl it is (branched C18), eicosyl (C20), docosyl (C22), tetracosyl (C24), cerul (C26), octacosyl (C28), melissyl (C30), dotriacontyl (C32) etc..
Include with about 40 straight chains of carbon atom of about 8- and the example of branched-alkyl derived from natural, but unlimited In it (is mainly all C to derive from hydrogenated groundnut, soybean oil and rapeseed oil18), h-tallow (C16-C18) etc. alkyl；And hydrogen The C of change10-C30Terpenol, such as hydrogenation geraniol (branched C10), hydrogenation fanesol (branched C15), hydrogenation phytol it is (branched C20) etc..
Suitable C2-C40The non-limiting example of alkyl-substituted phenyl includes octyl phenyl, nonyl phenyl, decyl benzene Base, dodecylphenyl, cetyl phenyl, octadecylphenyl, isooctyl phenyl, secondary butyl phenenyl etc..
Suitable C8-C40Carbocyclic ring alkyl include but not limited to derived from animal origin sterol for example cholesterol, lanosterol, The group of 7-DHC etc.；Group derived from plant origin, such as phytosterol, stigmasterol, campesterol etc.；With From the group of yeast sources, such as ergosterol, kryptosterol etc..Other suitable carbocyclic ring alkyl for use in the present invention are dredged Water end (W.E.) base includes but not limited to cyclooctyl, cyclo-dodecyl, adamantyl, decahydro naphthalene, and for example derived from natural carbon ring material The group of firpene, hydrogenation retinol, camphor, isoborneol alcohol etc..
The C of the aryl substitution enumerated2-C40Alkyl includes but not limited to styryl (for example, 2- phenethyls), hexichol second Alkenyl (for example, 2,4- diphenyl butyl), triphenylethylene base (for example, 2,4,6- triphenyl hexyls), 4- phenyl butyls, 2- first Base -2- phenylethyls, triphenyl vinyl phenol base etc..
Suitable C8-C80The non-limiting example of mixed ester includes, but are not limited to rilanit special, and (main 12- hydroxyls are hard The glyceryl ester of resin acid)；1,2- diacylglycerol ester, such as 1,2- distearyls glyceride, 1,2- cetearyl alcohols glyceride, 1, 2- myristyl glyceride etc.；Two, three or polyester of sugar, such as 3,4,6- tri- stearyl of glucose, fructose 2,3- February Osmanthus base ester etc.；And sorbitol ester, such as disclosed in United States Patent (USP) No.4,600,761 those, relevant disclosure exists This is incorporated by reference.
Useful monomer can be prepared by any method known in the art.See, e.g. United States Patent (USP) 4,421,902, 4,384,096,4,514,552,4,600,761,4,616,074,5,294,692,5,292,843,5,770,760 and 5, 412,142, relevant disclosure is incorporated by reference herein.
In one embodiment, the example of vinyl association (VA) monomer that can be employed in conjunction with the invention includes by formula Those of (V) indicate：
Wherein each R2It independently is H, methyl ,-C (O) OH or-C (O) OR3；R3It is C1-C30Alkyl；A is-CH2C(O) O- ,-C (O) O- ,-O- or-CH2O-；(R4-O)nIt is polyoxy alkylidene, is C2-C4The homopolymer of oxygroup alkylidene unit, nothing Copolymer or block copolymer are advised, wherein each R4It independently is C2H4、C3H6、C4H8Or they mixing and n be range in about 5- About 250, or about 5- about 100, or about 10- about 80, or even about 15- about 60 integer；And R5It is substituted or unsubstituted alkyl, It is selected from straight chain or branched C8-C40Alkyl, C8-C40Carbocyclic ring alkyl, C2-C40The C that alkyl-substituted phenyl, aryl replace2-C40 Alkyl and C8-C80Mixed ester, wherein R5Alkyl optionally include one in hydroxyl, alkoxy and/or halogen group or Multiple substituent groups.
In one embodiment, suitable vinyl association (VA) monomer of formula (V) includes, but are not limited to cetyl Polyethoxylated methacrylate ester (CEM), cetearyl polyethoxylated methacrylate ester (CSEM), the poly- second of stearyl Oxygroup (methyl) acrylate, eicosyl polyethoxylated (methyl) acrylate, docosyl polyethoxylated first Base acrylate (BEM), lauryl polyethoxylated methacrylate ester (LEM), cerul polyethoxylated (methyl) Acrylate, octacosyl polyethoxylated (methyl) acrylate, melissyl polyethoxylated (methyl) acrylate, Dotriacontyl polyethoxylated (methyl) acrylate, triphenyl vinyl phenol polyethoxylated methacrylate ester (TEM), Rilanit special polyethoxylated methacrylate ester (HCOEM), rapeseed oil polyethoxylated (methyl) acrylate and courage are solid Alcohol polyethoxylated methacrylate ester (CHEM), polyethoxylated part wherein in monomer include about 5- about 100 or about About 60 ethylene oxide repeating units of 10- about 80 or even about 15-.
In one embodiment, the VA monomer components in monomer mixture account for about 0.001wt%- about 25wt%, or about 0.01wt%- about 20wt%, or about 0.1wt%- about 15wt%, or even about 1wt%- about 10wt%, the gross weight based on monomer mixture Gauge.Herein and in the other places of description and claims, can combine individual numerical value (including value of carbon atoms), Or bound, form the additional range being not disclosed and/or do not address.
VS monomers：
It has been surprisingly found that vinyl surfactant (VS) monomer containing polyoxy alkylidene chain can be modified and contain There is the associative property of their multi-purpose polymer, to generate quality (texture) and rheological properties with high expectations The aqueous gel of energy.Although being not intended to be bound by any type theory, polyoxy alkylidene interference or the screen in VS monomers are thought The non-specific association between the hydrophobic grouping of associating monomer in polymer is covered, and weakens the associative property of the polymer in turn. The thickening effect of resulting polymers is adjusted in this VS monomers, and the rheologic behavio(u)r of polymer is optionally customized for selected application. Most surprisingly, it has been found that VS monomers assign rheology and aesthetic properties needed for aqueous gel, to provide than being free of VS The multi-purpose polymer of monomer is more soft, gel that is more smooth and can more sprawling.
Astoundingly, VS monomers are added in multi-purpose polymer and can be minimized or eliminate under mild method Visbreaking, and the shear shinning distribution (profile) of smooth outflow can be provided.
Polyoxyalkylene moieties (R8-O)vInclude specifically long-chain polyoxy alkylidene segment, it is single which is substantially similar to associations Hydrophilic segment in body.In one embodiment, polyoxyalkylene moieties (R8-O)vIncluding containing about 1- about 250 or even Polyoxyethylene, polyoxypropylene, polyoxy butylidene unit and the combination thereof of about 100 oxygen alkylidene units of about 5-.When When VS monomers include the oxygen alkylidene unit of more than one type, which can arrange according to random, non-random or block sequence Row.
Suitable VS monomers include, but are not limited to by those of formula (VI) expression：
Wherein each R6It independently is hydrogen or methyl ,-C (O) OH or-C (O) OR7；R7It is C1-C30Alkyl；A is-CH2C(O) O- ,-C (O) O- ,-O- or-CH2O-；P is that integer and r of the range in 0- about 30 are 0 or 1；Condition is that r is 0 when p is 0, and When p be range in the integer of 1- about 30 when r be 1；Wherein (R8-O)vIt is polyoxyalkylene group, C can be used as2-C4Oxygroup Homopolymer, random copolymer or the block copolymer of alkylidene unit arrange, wherein each R8It independently is C2H4、C3H6、C4H8、 Or they mixing and v be range in the whole of about 1- about 250 or about 4- about 100 or about 10- about 80 or even about 15- about 60 Number；And R9It is hydrogen or C1-C4Alkyl.
In one embodiment, suitable VS monomers include, but are not limited to the monomer with following chemical formula：
H2C=CH-O(CH2)aO(C3H6O)b(C2H4O)cH;
H2C=CHCH2O(C3H6O)d(C2H4O)eH;
H2C=C(Q)-C(O)-O(CH2)aO(C3H6O)b(C2H4O)cH；Or
H2C=C(Q)-C(O)-O(C3H6O)d(C2H4O)eH
Wherein Q is hydrogen or methyl；A is 2,3 or 4；B is range in 1- about 20 or about 2- about 10 or even about 3- about 7 Integer；C is integer of the range in about 5- about 50 or about 8- about 40 or even about 10- about 30；D be range in 1- about 20 or about The integer of 2- about 10 or even about 3- about 7；With e be range about 1- about 50 or even about 5- about 40 or even about 10- about 25 integer.In another embodiment, b or c can be 0.In still another embodiment, d or e can be 0.
The example of suitable VS monomers includes, but are not limited to by Clariant Corporation with trade nameR109, R208, R307, RAL 100, RAL109, RAL208 and RAL307 sell commercially available polymerizable Emulsifier；By Bimax, the BX-AA-E5P5 of Inc. sale；And combinations thereof.In another embodiment, suitable VS monomers packet It includes, but is not limited to,R208, R307 and RAL307.
According to manufacturer：R109 is that empirical formula is CH2=CH-O(CH2)4O(C3H6O)4(C2H4O)10H Random ethoxylated/propoxylated 1,4- butanediol vinyl ethers；R208 is that empirical formula is CH2=CH- O(CH2)4O(C3H6O)4(C2H4O)20The random ethoxylated/propoxylated 1,4- butanediol vinyl ethers of H；R307 is that empirical formula is CH2=CH-O(CH2)4O(C3H6O)4(C2H4O)30The oxygen of the random ethoxylation of H/third Base 1,4- butanediol vinyl ethers；RAL109 is that empirical formula is CH2=CHCH2O(C3H6O)4(C2H4O)10The random ethoxylated/propoxylated allyl ether of H；RAL208 is that empirical formula is CH2=CHCH2O (C3H6O)4(C2H4O)20The random ethoxylated/propoxylated allyl ether of H；RAL307 is empirical formula For CH2=CHCH2O(C3H6O)4(C2H4O)30The random ethoxylated/propoxylated allyl ether of H；It is experience with BX-AA-E5P5 Formula is CH2=CHCH2O(C3H6O)5(C2H4O)5The random ethoxylated/propoxylated allyl ether of H.
In one embodiment, the suitable VS monomers that can be employed in conjunction with the invention include, but are not limited to polyoxy Asia Alkyl diol mono allyl ether is (for example, CH2=CHCH2(OCH2CH2)nOH, such as poly-dihydric alcohol A350 (Mw=350)；Poly-dihydric alcohol A500(Mw=500)；And/or poly-dihydric alcohol A1100 (Mw=1100)；And/or CH2=CHCH2(OCH2CH2)n(OCH2CHCH3)mOH, Such as poly-dihydric alcohol A31/1000-EO:The ratio between PO is 3:1(Mw=1000)；Poly-dihydric alcohol A32/550-EO:The ratio between PO is 3:2 (Mw=550)；Poly-dihydric alcohol A11/1800-EO:The ratio between PO is 1:1(Mw=1800)；Poly-dihydric alcohol A91/550-EO:The ratio between PO is 3:2(Mw=550)；Poly-dihydric alcohol A11-4-EO:The ratio between PO is 3:1(Mw=750)；And/or poly-dihydric alcohol A 20-20-EO:PO it Than being 1:1(Mw=2100)；Polyether polyols mono vinyl ether is (for example, CH2=CH(OCH2CH2)nOH, such as poly- binary Alcohol R-500 (Mw=500)；Poly-dihydric alcohol R-1100 (Mw=1100)；And/or poly-dihydric alcohol R-5000 (Mw=about 6000)), poly- second Glycol monomethyl ether monomethacrylates are (that is, CH3(OCH2CH2)nOCOC(CH3)=CH2, such as Genagen M 750MA (Mw =810-870) and/or Genagen M 1100MA (Mw=1160-1220)) or any of which two or more suitable Mixture.
The amount of the VS monomers used in the multi-purpose polymer for preparing the present invention can vary widely, and especially depend on The final rheologic behavio(u)r needed for polymer.When in use, in one embodiment, monomer reaction mixture contain to One or more VS monomers of few about 0.01wt%, the total weight based on monomer mixture, or even at least about 0.1wt% it is a kind of or A variety of VS monomers, the total weight based on monomer mixture.In one embodiment, monomer mixture includes and is not greater than about The VS monomers of 25wt% are not greater than about the VS monomers of 20wt%, are not greater than about the VS monomers of 15wt%, mono- no more than about the VS of 10wt% Body, or it is even no greater than the VS monomers of about 7.5wt%, the total weight based on monomer mixture.In another embodiment, monomer Mixture includes about 0.01wt%- about 25wt%, or about 0.1wt%- about 20wt%, or about 0.5wt%- about 15wt%, or about 1wt%- is about 10wt%, or even about 2wt%- about 7.5wt% VS monomers, the total weight based on monomer mixture.Herein and in specification and In the other places of claim, individual numerical value (including carbon atom number value) or bound can be combined, formed it is additional not Range that is open and/or not addressing.
Polymerizable silicone macromonomer (PSM)：
The multi-purpose polymer of the present invention can be mixed by the monomer containing one or more of polymerizable siloxane macromonomers Object is closed to prepare, the polymerizable siloxane macromonomer have one containing one or more polyoxy alkylidene repetitive units or Multiple side chains or branch.The siloxanyl monomers that can be employed in conjunction with the invention can be expressed from the next：
Wherein each R20Independently selected from straight chain or branched C1-C30Alkyl, C4-C20Aryl or C2-C20Alkenyl；Wherein (R8-O)vIt is polyoxyalkylene group, C can be used as2-C4Homopolymer, random copolymer, the block of oxygroup alkylidene unit Copolymer form arranges, wherein each R8It independently is C2H4、C3H6、C4H8Or their mixture and v be range about 1- about The integer of 250 or about 4- about 100 or about 10- about 80 or even about 15- about 60；X is integer of the range in 0- about 200；Y is Integer of the range in 0- about 200；It is integer of the range in 1- about 200 with z；Wherein G, which is selected from, contains at least one free redical Any group of the carbon-carbon double bond of polymerization.
G is selected from any group of the carbon-carbon double bond containing free redical polymerization.In one embodiment, G is by siloxanes The residue that the esterification of polyalcohol and the reactant of carbon-carbon double bonds or etherification reaction obtain.After esterification or etherificate, siloxanes is big Molecule monomer is aggregated in the main chain of the multi-purpose polymer of the present invention, and carbon-carbon double bond keeps complete and can be used for radical polymerization It closes.In another embodiment, the reactant containing carbon-carbon double bond be selected from cyclic acid anhydride (for example, itaconic anhydride, citraconic anhydride, Maleic anhydride and its isomers), (methyl) acrylic acid, vinyl alcohol and allyl alcohol.In still another embodiment, G can be by The residue that following formula indicates：
Wherein under this concrete condition, R indicates hydrogen and methyl, and open chemical bond lines indicate and copolymeric siloxane The covalent bond that oxygen atom on alcohol is formed.
The acid anhydrides that terminal hydroxy group on copolymeric siloxane alcohol provides respectively with cyclic acid anhydride and (methyl) propylene acid reaction Or esterification occurs between carboxylic acid group.Equally, the terminal hydroxy group on copolymeric siloxane alcohol and on vinyl or allyl alcohol Hydroxyl between etherification reaction occurs.Esterification and etherification reaction are well-known in the art.In PCT Publication WO2007/ Copolymeric siloxane alcohol is disclosed in 101048 and cyclic acid anhydride reacts the siloxane macromer to form free redical polymerization, it should Document is incorporated by reference herein.
In esterification between copolymeric siloxane alcohol disclosed above and cyclic acid anhydride, polymerizable siloxane is depicted The half ester or monoesters of macromonomer.In this embodiment, after esterification, remaining carboxyl functional group is retained in On group by cyclic anhydride residue contribution.Equally within the scope of the present invention, can by adjust the stoichiometry of reactant with So that remaining carboxyl is reacted with the terminal hydroxy group provided by the second copolymeric siloxane alcohol, obtains siloxane macromer diester, from And form two ester large molecule of siloxanes.
In another embodiment, each R20Independently selected from straight chain or branched C2-C20Alkyl, C5-C14Aryl or C3-C15 Alkenyl；Wherein a is integer of the range in 1- about 50；B is integer of the range in about 1- about 50；X is range in the whole of 1- about 100 Number；Y is integer of the range in 1- about 100；It is integer of the range in 2- about 100 with z；Wherein G is as defined above.Another real It applies in scheme, each R20Independently selected from straight chain or branched C3-C10Alkyl, C6-C10Aryl or C4-C10Alkenyl；Wherein a is range In the integer of 5- about 25；B is integer of the range in about 5- about 25；X is integer of the range in 5- about 50；Y is range in 5- about 50 Integer；It is integer of the range in 5- about 50 with z；Wherein G is as defined above.Herein and in description and claims In other places, individual numerical value (including value of carbon atoms) or bound can be combined, is formed additional undisclosed and/or not The range addressed.
In one embodiment, PSM monomers account for about 0.01wt%- about 10wt%, or about 0.1wt%- about 7.5wt%, or about 0.5wt%- about 5wt%, or even about 1wt%- about 2.5wt%, the total weight based on monomer mixture.Herein and in specification In the other places of claim, individual numerical value (including value of carbon atoms) or bound can be combined, formed it is additional not Range that is open and/or not addressing.
XL monomers：
The multi-purpose polymer of the present invention can be by containing for introducing branched and control molecular weight one or more of friendships It is prepared by the monomer mixture of receipts or other documents in duplicate body.Suitable how unsaturated crosslinking agent is well-known in the art.Carrying can also be used to exist Before polymerization, among or can cause the single unsaturated compound for being formed by the reactive group that copolymer crosslinks later. Other useful cross-linking monomers include containing multiple reactive groups such as epoxy group, isocyanate group and hydrolyzable silane base Polyfunctional monomer.It can use various polyunsaturated compounds with generating portion or substantially crosslinked three-dimensional network.
The example of suitable how unsaturated crosslinking monomer component includes, but are not limited to how unsaturated aromatic monomer, such as two Vinyl benzene, divinyl naphthalene and trivinylbenzene；How unsaturated alicyclic monomer, such as 1,2,4- triethylene cyclohexanes； The bifunctional ester of phthalic acid, such as diallyl phthalate；How unsaturated aliphatic monomers, such as alkadienes, triolefin Hydrocarbon and alkatetraenes, including isoprene, butadiene, 1,5- hexadienes, 1,5,9- last of the ten Heavenly stems triolefins, 1,9- decadinene, 1,5- heptan Diene etc..
Other suitable how unsaturated cross-linking monomers include, but are not limited to polyene-based ether, such as triallyl pentaerythritol Ether, diallyl pentaerythrite ether, diallyl sucrose ether, eight allylsucrose ethers and trimethylolpropane allyl ether； The how unsaturated ester of polyalcohol or polyacid, such as two (methyl) acrylic acid 1,6- hexylene glycols ester, tetramethylene three (methyl) third Olefin(e) acid ester, (methyl) allyl acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, three (methyl) acrylic acid trimethylolpropane base ester, two (methyl) acrylic acid trimethylolpropane base esters and two (first of polyethylene glycol Base) acrylate；Alkylenebisacrylamides, such as methylene-bisacrylamide, propylidene bisacrylamide etc.；Di-2-ethylhexylphosphine oxide The hydroxyl and carboxy derivatives of acrylamide, such as the bis- methylol methylene-bisacrylamides of N, N`-；Polyethylene glycol two (methyl) Acrylate, such as ethylene glycol two (methyl) acrylate, (methyl) acrylate of diglycol two and two three second two of contracting Alcohol two (methyl) acrylate；How unsaturated silane, such as dimethyl divinyl silane, methyl trivinyl silane, allyl Base dimethylvinylsiloxy base silane, diallyldimethylsilane and tetravinyl silane；How unsaturated stannane, such as tetraallyl Tin and diallydimethyl tin etc..
The useful single unsaturated compound for carrying reactive group includes N hydroxymethyl acrylamide；N- alkoxy (first Base) acrylamide, wherein alkoxy is C1-C18Alkoxy；With unsaturated hydrolyzable silane, such as triethoxy vinyl silicon Alkane, three isopropoxy vinyl silanes and methacrylic acid 3- triethoxysilylpropyltetrasulfide esters etc..
Useful multifunctional cross-linking monomer containing multiple reactive groups includes, but are not limited to hydrolyzable silane, such as Ethyl triethoxysilane and ethyl trimethoxy silane；The hydrolyzable silane of epoxy group substitution, such as 2- (3,4- epoxy basic rings Hexyl) ethyl triethoxysilane and 3- glycidoxy-propyltrimethoxy silanes；Polyisocyanates, such as Isosorbide-5-Nitrae-diisocyanate Ester group butane, 1,6- diisocyanatohexanes, 1,4- phenylene diisocyanates and 4,4 '-oxygroups are bis- (phenyl isocyanate)；No It is saturated epoxides, such as glycidyl methacrylate and allyl glycidyl ether；Polyepoxide, such as two contractings Water glyceryl ether, 1,2,5,6- bicyclic oxygens hexane and ethylene glycol diglycidyl base ether etc..
The how unsaturated crosslinking agent of ethoxylated polyalchohols such as glycol, triol and bisphenols is equally usefully derived from, The ethoxylated polyalchohols with about 2- about 100mol ethylene oxide/mol hydroxy functional groups come ethoxylation and with it is polymerizable not Saturated group sealing end such as vinyl ethers, allyl ether, acrylate, methacrylate.The example packet of this crosslinking agent Include bisphenol A ethoxy dimethylacrylate；Bisphenol F ethoxylated dimethacrylate, ethoxylation trihydroxy methyl third Alkane trimethyl acrylic ester etc..It is special that other ethoxylation crosslinking agents of multi-purpose polymer for use in the present invention are included in the U.S. Sharp No.6, crosslinking agent derived from polyalcohol disclosed in 140,435, relevant disclosure are incorporated by reference herein.
The example for the XL monomers being particularly suitable includes, but are not limited to have at least two acrylate or methacrylic acid The acrylate and methacrylate of the polyalcohol of ester group, such as trimethylolpropane trimethacrylate (TMPTA), ethyoxyl 3 trimethylolpropane trimethacrylates (TMPEO 3TA) changed, 15 trimethylolpropane trimethacrylates of ethoxylation (TMPEO15TA), trimethylolpropane dimethacrylate, triethylene-glycol dimethylacrylate (TEGDMA), second Oxygroup (30) bisphenol a dimethacrylate (EOBDMA)；Polyene-based ether (APE), such as triallyl pentaerythritol, diene Propyl pentaerythrite and trimethylolpropane allyl ether (TMPDAE)；Cane sugar allyl ether (AS), such as diallyl sugarcane Sugar ether, eight allylsucrose ethers；Alkylenebisacrylamides, such as methylene-bisacrylamide (MBA), the double acryloyls of propylidene Amine；With the suitable mixture of any two or more in them.
In use, amount of the cross-linking monomer in monomer mixture is most about 5wt%, the gross weight based on monomer mixture Amount.In another embodiment, the amount range of XL monomers is in about 0.001wt%- about 5wt%, or about 0.01wt%- about 4wt%, Or about 0.05wt%- about 3wt%, or about 0.1wt%- about 2wt%, or even about 0.5wt%- about 1wt% monomer mixture, based on single The total weight of body mixture.Herein and in the other places of description and claims, can combine individual numerical value (including Carbon atom number value) or bound, form the additional range being not disclosed and/or do not address.
Chain-transferring agent：
The multi-purpose polymer of the present invention comprising the well-known one or more chains of polymer arts optionally by turning It is prepared by the monomer mixture for moving agent (CTA).
Without limitation, the suitable chain-transferring agent being used in the present invention is selected from various containing thio and disulphide change Close object, such as C1-C18Alkyl hydrosulfide, mercaptan carboxylic acid, mercapto-carboxylic ester, thioesters, C1-C18Alkyl disulfide, aryl curing Object, multi-functional thiol etc.；Phosphite ester (salt) and phosphinate (salt)；Halogenated alkyl compounds, such as carbon tetrachloride bromine trichlorine Methane etc.；With unsaturated chain transfer agent, such as α-methylstyrene.
Multi-functional thiol includes trifunctional mercaptan, such as trimethylolpropane tris (3-thiopropionate), tetrafunctional mercaptan, Such as pentaerythrite four (3-thiopropionate), pentaerythrite four-(thioglycolic acid esters) and four (thiolactic acid of pentaerythrite Ester)；Six functional thiols, such as dipentaerythritol six (thioglycolic acid esters) etc..
Alternatively, chain-transferring agent can reduce any of addition polymers molecular weight during the free radical polymerization of vinyl monomer Catalytic chain transfer agent.The example of catalytic chain transfer agent includes such as cobalt complex (for example, cobalt (II) chelating agent).It is catalyzed chain tra nsfer Agent can often be used with the relatively low concentration relative to mercapto CTA.
The example of suitable chain-transferring agent includes, but are not limited to octyl mercaptan, n-dodecyl mercaptan, tertiary dodecyl Mercaptan, hexadecyl mercaptan, Stearyl mercaptan (ODM), 3- mercaptopropionic acids isooctyl acrylate (IMP), 3- mercaptopropionic acids butyl ester, 3- Mercaptopropionic acid, thioglycolic acid butyl ester, isooctyl thioglycolate, thioglycolic acid dodecyl ester etc..It can be by chain-transferring agent It is added in monomer reaction mixture, amount is up to the polymerizable monomer mixture of about 10wt%, based on the total of monomer mixture Weight.When it is present, chain-transferring agent accounts for at least about 0.05wt% of mixture, the total weight based on monomer.Herein and illustrating In the other places of book and claim, individual numerical value (including value of carbon atoms) or bound can be combined, is formed additional The undisclosed and/or range do not addressed.
Multi-purpose polymer and its production method
The present invention multi-purpose polymer can by typical polymerization technology, such as by emulsion polymerization, inverse emulsion polymerization, Polymerisation in solution, precipitation polymerization, bulk polymerization and dispersin polymerization synthesize, these polymerization techniques are that polymer arts are well-known 's.
In one embodiment of the invention, polymerization multi-purpose polymer is made from it monomer and passes through emulsion polymerization, institute Stating emulsion polymerization can carry out in the form of simple batch technology, in the form of the adding technology of metering, or reaction can be with small Batch causes, and then a large amount of monomers can be continuously metered in reactor (seed technique).Typically, polymerization technique is in model It is trapped among under about 20 DEG C-about 95 DEG C of reaction temperature and carries out, however, higher or lower temperature can be used.It is convenient for monomer to have The emulsification of mixture, emulsion polymerization carry out in the presence of at least one surfactant.In one embodiment, with lotion Based on total weight, amount be about 1wt%- about 10wt% or range in about 3wt%- about 8wt% or even range in about 5wt%- Emulsion polymerization is carried out in the presence of the surfactant of about 7wt%.It, can group herein and in the other places of description and claims Individual numerical value (including value of carbon atoms) or bound are closed, the additional range being not disclosed and/or do not address is formed.
Emulsion polymerization reaction mixture further includes one or more of radical initiators.In one embodiment, one The amount range of kind or more radical initiator is in about 0.01wt%- about 3wt%, the total weight based on monomer.Polymerization can To be carried out at the neutral pH alkaline to appropriateness in aqueous or aqueous alcohol medium.
In typical polymerization, in suitable reactor, under mixing, monomer mixture is added to suitable To prepare monomer emulsions in the solution of emulsifying surfactant such as nonionic surfactant in the water of amount, implement at one In scheme, the surfactant is straight chain or branched alcohol b-oxide or nonionic surfactant and anion The mixture of surfactant (such as aliphatic alcohol sulfate or alkylsulfonate).By any convenient method, such as pass through With nitrogen scrubbing, make lotion deoxidation, then by add polymerization catalyst (initiator), such as sodium peroxydisulfate or it is any its Its suitable addition polymerization catalyst (well-known in such as emulsion polymerization field), initiated polymerization.It is stirred to react, until polymerization It completes, typically time range was in about 4- about 16 hours.Monomer emulsions can be optionally heated to range about 20 DEG C-about 95 DEG C of temperature, adds initiator later.It can be disappeared by adding more catalyst (such as emulsion polymerization field is well-known) Except unreacted monomer.Then resulting polymers emulsion product is discharged from reactor, and packs for storing or using.Optionally Ground, can be in the pH or other physics and chemical characteristic for adjusting lotion before being discharged in reactor.Typically, product emulsion Total solid (TS) content range is about 10wt%- about 60wt%.Typically, polymer content total in product emulsion is ranging from about 15wt%- about 50wt%, generally no greater than about 40wt%.Herein and in the other places of description and claims, it can combine individually Numerical value (including value of carbon atoms) or bound, form range that is additional undisclosed and/or not addressing.
Promote the table that the suitable surfactant of emulsion polymerization includes non-ionic, anion, both sexes, cationic Face activating agent and their mixture.Most commonly, using nonionic and anion surfactant or their mixing Object.As known in the art, in being changed by the hydrophobic and hydrophilicity of suitably selected emulsifying surfactant The physical property (for example, viscosity, can spreadability, clarity, quality etc.) of the polymer of sum.
Be suitable for promoting the nonionic surfactant of emulsion polymerization is polymer arts it is well known that and including but not It is limited to straight chain or branched alcohol b-oxide, C8-C12Alkyl phenol alkoxylate, such as octyl phenol b-oxide, polyoxy are sub- Ethyl polyoxypropylene block copolymer etc..Other useful nonionic surfactants include the C of polyoxyethylene glycol8- C22Aliphatic ester, single and two glyceride, sorbitan ester and ethoxyquin sorbitan ester, C8-C22Aliphatic acid fat Sour diol ester, HLB value are greater than about 12 ethylene oxide and the block copolymer of propylene oxide, ethoxylated octyl phenol and it Combination.
Suitable alkyl phenol alkoxylate surfactant includes, but are not limited to by Rhodia, and Inc. is with trade nameThe octyl phenol of CA-897 sale.In another embodiment, straight chain alcohol alkoxide includes by BASF Corp. With trade nameC-17、 A-38 andThe cetostearyl alcohol of A-39 sale The polyglycol ether of (mixture of cetyl alcohol and stearyl alcohol).In still another embodiment, polyoxyethylene polyoxy Asia third Group block copolymer includes by BASF Corp. with trade nameF127 andL35 sale Copolymer.
Other suitable nonionic surfactants include, but are not limited to ethoxylated linear fatty alcohol, such asA 5060 (Cognis), Ethal LA-23 and EthalLA-50 (Ethox Chemicals), branched-alkyl Ethoxylate, such asX1005 (Clariant Corp.), secondary C12-C14Alcohol b-oxide, such asS15-30 and S15-40 (Dow Chemical Co.), the surface-active based on ethoxylated octyl phenol Agent, such asX-305, X-405 and X-705 (Dow Chemical Co.),CA 407,887 and 897 (Rhodia, Inc.),OP 3070 and 4070 (BASFCorp.),OP 30 and 40 (Uniqema), the block copolymer of ethylene oxide and propylene oxide, such asL35 and F127 (BASF ) and secondary C Corp.11Alcohol b-oxide, such asEPN 407(Clariant Corp.).In trade literature In can find many other suppliers.
The anion surfactant for being suitable for promotion emulsion polymerization is polymer arts it is well known that and including bay Base sodium sulphate, neopelex, dioctyl sodium sulphosuccinate, di-sec-butyl sodium naphthalene sulfonate, dodecyl diphenyl Ether sulfonic acid disodium and n-octadecane base disodium sulfosuccinate etc..
The suitable polymer stabilizer (also referred to as protecting colloid) of emulsion polymerization technique for the present invention is water-soluble Polymer, including such as synthetic polymer, such as polyvinyl alcohol, the polyvinyl acetate of partial hydrolysis, polyvinyl pyrrole Alkanone, polyacrylamide, polymethacrylamide, the addition polymers of carboxylate function, poly- alkyl vinyl ether etc.；Water-soluble natural Polymer, for example, gelatin, pectin, alginates, casein, starch etc.；And modified natural polymers, such as methylcellulose, hydroxyl The hydroxyethyl cellulose etc. that propyl cellulose, carboxymethyl cellulose, allyl are modified.In some cases, it may be advantageous to use Synthesize the mixture with natural protecting colloid, such as the mixture of polyvinyl alcohol and casein.Further suitable natural polymerization Object is compound ether, such as methyl hydroxyethylcellulose and carboxy methyl cellulose.Polymer stabilizer can be to be based on lotion Total weight most about 10wt%, or the total weight based on lotion most about 7.5wt% or most about 5wt% or most about The amount of 2.5wt% or most about 2wt% use.In another embodiment, when in use, polymer stabilizer to be based on lotion Total weight about 0.001wt%- about 10wt%, or about 0.01wt%- about 7.5wt%, or about 0.1wt%- about 5wt%, or about 0.5wt%- about 2.5wt%, or even about 1wt%- about 2wt%, amount includes.Herein and in the other places of description and claims In, individual numerical value (including carbon atom number value) or bound can be combined, is formed additional undisclosed and/or not described And range.
Polymer stabilizer used according to the invention, when they are miscible in any proportion in water or in 20 DEG C of water Solubility be at least about 0.1wt% and when be diluted with water under aforementioned temperature do not precipitated from these aqueous solutions when, be referred to as It is water-soluble.The molecular weight ranges of water-soluble synthetic polymer stabilizer are typically about 5,000- about 2, and 000,000, or about About 1,500,000 dalton of 25,000-.Under the concentration of about 2%- about 10wt% and at a temperature of about 20 DEG C, polymer stabilizer The range of viscosities of aqueous solution be typically about 1- about 10,000mPas.Herein and in the other places of description and claims In, individual numerical value (including carbon atom number value) or bound can be combined, is formed additional undisclosed and/or not described And range.
Useful polymer stabilizer is the hydroxyethyl cellulose that allyl is modified, such as obtained from Clariant'sAM-HEC grades.Reactive allyl in side chain increases the grafting ability of cellulose ether, to be stablized Lotion.Stabilizer is the hydroxyethyl cellulose powder that allyl is modified (granularity is less than 180 microns)AM H40YP2(AMHEC)。
Exemplary radical initiator includes, but are not limited to water-soluble inorganic persulfate compound, such as persulfuric acid Ammonium, potassium peroxydisulfate and sodium peroxydisulfate；Peroxide, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide and peroxidating Lauryl；Organic hydroperoxide, cumene hydroperoxide and t-butyl hydroperoxide；Organic peracid, such as peracetic acid；It is molten with oil Free love base generates reagent, such as 2, the suitable mixture of 2 '-azodiisobutyronitriles etc. and two or more in them.It crosses Oxide and peracid can be optionally with reducing agent such as sodium hydrogensulfite or ascorbic acid, sulfinate derivants for exampleFF6 and FF7 (Br ü ggemann Chemical) transition metal, hydrazine etc. are activated.In an embodiment In, suitable radical polymerization initiator includes, but are not limited to water-soluble azo polymerization initiator, such as has on alkyl Bis- (tertiary alkyl) compounds of 2,2 '-azos of water solubilising substituent.In another embodiment, azo polymerization catalyst includes, But it is not limited to, obtained from DuPont'sRadical polymerization initiator, such as44 (2,2'- azos it is bis- (2- (4, 5- glyoxalidine base) propane),56 (two hydrochloric acid 2,2'- azos are bis- (2- methyl-props amidine (propionamidine))), With68 (4,4'- azos are bis- (4- cyanopentanoic acids)).
Optionally, the well-known other emulsion polymerization additives in emulsion polymerization field, such as solvent, buffer, chelating Agent, inorganic electrolyte, chain terminating agent and pH adjusting agent may be embodied in polymerization system.
A kind of suitable general emulsion polymerisation process presented below for preparing multi-purpose polymer of the present invention.
In one embodiment, it in the reactor equipped with nitrogen inlet and blender, under nitrogen atmosphere and is mixing Under stirring, by nonionic surfactant containing emulsifying amount or nonionic surfactant and anion surfactant Mixture suitable quantity of water in the desired amount of each monomer is merged to prepare monomer emulsions.It is mixed by the monomer of types described above The stirring extent that object is formed required by lotion is well known to the skilled person.By known in the art any suitable Method, such as by with nitrogen scrubbing, making the lotion being thusly-formed substantially deoxidation, then, under continuous be mixed, Radical initiator is added in the lotion, polymerization is caused.It can optionally, before or after adding initiator, by lotion Temperature adjusts the temperature to range at about 20 DEG C-about 60 DEG C.After adding initiator, typically telo merization mixture Temperature of the temperature to range at about 60 DEG C -95 DEG C, and the time that such temperature is enough to complete polymerization is maintained at, typically about 3- about 14 hours.Optionally, it can destroy or further polymerize unreacted by adding various redox reagents or catalyst Residual monomer.Then gained polymerized emulsion can be cooled down, and is discharged and collects from reactor.
The technical staff of polymer arts will realize the amount of adjustable each monomer component, and obtaining has any required list The polymer of body component ratio.Also the water of variation ratio can optionally be used.Solvent miscible with water, such as alcohol and as described above Other polymeric additives also are included in reaction mixture.Suitable alcohol includes, but are not limited to dihydric alcohol, such as ethylene glycol, Propylene glycol, butanediol, hexylene glycol, glycerine etc..
In one embodiment, it is solid can be prepared into the total polymer comprising about 1%- about 60% for resulting polymer lotion Body, either the total polymer solid of the total polymer solid of about 10%- about 40% or even about 15%- about 25%, are based on poly- Close the weight of object.Herein and in the other places of description and claims, individual numerical value can be combined (including carbon atom A numerical value) or bound, form the additional range being not disclosed and/or do not address.In any with before, what is produced is poly- The pH ranges for closing object lotion are typically greater than or are equal to about 7, and Brookfield viscosity at ambient temperature is not greater than about 100mPa.s (spindle #2,20rpm).
Optionally, if it is expected acid pH, pH can be adjusted to ranging from by with acid material such as organic acid, inorganic acid About 1, to the numerical value no more than about 7, is further processed produced multi-purpose polymer lotion.Multi-purpose polymer lotion is typical Ground is swollen, and forms flowable and sprayable smooth, sticky solution, or the neutral gelling for arriving acid pH, and the polymerization Object is usually substantially stablized under such pH value.Multi-purpose polymer lotion can use water or solvent to dilute, or pass through steaming Concentration of sending out water a part of.Alternatively, can be by using equipment well-known in the art such as spray dryer, drum dried Gained multi-purpose polymer lotion is substantially dried to powder or crystal form by device, freeze-dryer etc..
The present invention multi-purpose polymer can for example by emulsion polymerization, polymerisation in solution, precipitation polymerization, bulk polymerization, It is prepared by dispersin polymerization, and optionally by be added various additives knowns and conven-tional adjuvants and solvent in addition to water come It uses.When selecting emulsion polymerization as polymerization technique, polymerisation can be carried out by interval and semi-batch technology.
The multi-purpose polymer of the present invention is in deionized water in the pH ranges of about 1- about 7 under the weight concentration of about 2wt% In and/or acid form under can provide ranging from about 300mPas- about 100,000mPas or bigger Brookfield it is viscous It spends (Brookfield RVT, 20rpm, under about 25 DEG C of ambient room temperature).
Molecular weight (weight is equal) range of the multi-purpose polymer of the present invention is about 5,000 dongles in one aspect of the invention Dun-about 10,000,000 dalton are about 10 in another aspect of this invention, 000 dalton-about 5,000,00 dalton, and It is about 50 in the further aspect of the present invention, 000 dalton-about 3,000,000 dalton, this uses polystyrene standards Pass through gpc measurement.
The multi-purpose polymer of the present invention can be in personal nursing, health care, residential care, public organizations and industry In the various products of (being referred to as " I＆I ") nursing, and used in the various products of medical treatment and commercial Application.The present invention's is multi-purpose Way polymer can be used as improving the efficiency of chemistry and physiologically active ingredient and cosmetic, deposition or delivery efficiency emulsifier, Stabilizer, suspending agent, deposition aid, film forming agent, rheology modifier, hair styling agents adjust setting agent, conditioner, humidification Auxiliary agent, carrier, and the examination as the physiological sensing and aesthetic properties for improving the preparation that they are contained within are sprawled in agent Agent.In addition, the cationic character of the multi-purpose polymer of the present invention makes these polymer can be used as antistatic agent, and at some Under the conditions of, biocidal, antibacterial, anti-corrosion and antimicrobial acivity can be also provided.
Method：
Viscosity：Use Brookfield rotary spindles viscosimeter (Brookfield Engineering Laboratories, Inc., RVT type) at 20 revs/min (rpm) under about 20 DEG C-about 25 DEG C of ambient room temperature, with milli Pa Sec (mPas) (cP) is the record viscosity (being known as Brookfield viscosity) that unit measures the composition containing each polymer. According to the viscosity table that manufacturer provides, select for spindle size used in specific viscosity measurement.
" dilute or low viscosity " is typically meant that the drumped flowing product of viscosity most about 1000mPas, " medium Viscosity " refers to the product that range of viscosities arrives about 3,000mPas higher than 1,000；" high viscosity " refers to that range of viscosities is higher than 3,000 To the product of about 10,000mPas；" gel " refers to the product that viscosity is more than 10,000mPas, unless otherwise indicated.
Yield value：Yield value is defined as the initial resistance flowed under stress.It is by using Brookfield viscosimeters (Model RVT) is measured with Brookfield yield values (BYV) Extrapolation method.Using Brookfield viscosimeters, measurement exists Pass through the torque needed for fluid sample rotary spindle under the speed of 0.5-100rpm.Torque reading is multiplied by the suitable of spindle and speed Constant obtains apparent viscosity.Yield value is the extrapolated value that measured value is 0 to shear velocity.BYV is calculated by following the equation：
BYV,dyn/cm2=(ηα1-ηα2The wherein η of)/100α1And ηα2=in two different spindle speed (it is 0.5rpm respectively And 1.0rpm) under the apparent viscosity that obtains.The validity that these technologies and yield value measure is in Lubrizol Advanced (the revision of technical data sheet the 244th of the Noveon Consumer Specialties Division of Materials, Inc.: 5/98) it is explained in, the document is incorporated by reference herein.Lower yield value (<50dyns/cm2) indicate smooth and newton shape flowing Performance.
Clarity：When record, at least about 24 hours after manufacturing composition, pass through 920 colorations of Brinkmann PC Meter measures the clarity of the composition containing polymer with %T (light transmittance).Using deionized water as reference, clarity measurement is carried out (clarity range 100%).The composition that clarity is about 60% or more is substantial transparent；Clarity range is about The composition of 45%-59% is judged as YES substantially translucent.
D. turbidity：When record, using Nephelometric nephelometers, use distilled water (NTU=0) as reference substance, The turbidity of the composition containing polymer is measured in Nephelometric turbidity units (NTU).NTU values are about 90 or higher groups It closes object and is judged as muddiness.
E. stability：The stabilization of the composition of polymer product lotion or preparation is evaluated by one or more following processes Property.
Storage：The sample of test products stores at one or more following temperature：(a) ranging from about 20 DEG C-about 25 DEG C environment temperature under at least 1 week arrive the most about 6 months time；(b) in baking oven, at elevated temperatures, exist in range Most about 5 weeks time (accelerated ageing storage) (unless otherwise indicated) at a temperature of about 30 DEG C-about 50 DEG C of selection.
By the periodically visually visible sedimentation of the stored sample of observation, or in the time of selection as described in following samples Apparent measurable Brookfield viscosity of measuring space increases, to determine stability.In ambient temperature storage, about In 2 months whole storage times, daily visual detection sample, is then detected, and every two weeks later most about 6 in one week It is monthly detected in a month whole storage times.Under each storage temperature, if：(a) sedimentation is not observed, if occurring Some are settled and it is not more than about the 2% of population of samples product；(b) product viscosity does not increase, if increase, but increase Add and be not greater than about 100mPas, then judges that composition is stable.
F. pass through the aqueous amine solution of acid base titration：With 1:In excessive water (1 under 1 weight ratio:10 molar ratios) in each list Body carries out acid base titration, periodically tracks its hydrolytic stability 1 or 2 weeks.It is expected that 100% hydrolysis of amine monomers obtains 1mol amine alcohols With 1mol methacrylic acids, this can be measured (acid value, mg KOH/g) by acid base titration.
G. suspend test step：From the point of view of product efficiency and appearance, polymeric system suspended active and/or aesthetics The insoluble oily of upper pleasant and the ability of bulk material are important.Using the transparent bath gel sample prepared in table 4, survey Try suspending power.The mark of 50mm is arrived with bath gel test preparation filling 6 dram (dram) bottle (about 70mm high × 25mm diameters) Note.Disperse in entirely bath gel sample aesthstic bead (Unispheres UEA-509 are obtained from Induchem AG, Switzerland, composition：Lactose, cellulose, hydroxypropyl methyl cellulose), and take pictures, to determine bead rising in gel Beginning position.Bottle is placed in the time of aging 12 weeks in 45 DEG C of baking ovens.At the end of 12 weeks oven test time, sample is detected The suspendability of middle bead.It is suspended as a result, wherein using the grade visual evaluation of 4-0：4=coagulated relative to starting bead position It is not settled significantly in glue, 3=relative to starting bead position slightly sedimentation or distance of fall less than about 1/4,2=relative to Originate the distance of fall of bead position about 1/4,1=be more than under 1/4 relative to the initial position in bath gel and fall on 1/2 downthrow From and 0=relative to bath gel in initial position be more than 1/2 distance of fall.
H. molecular weight determination：Had by what Polymer Laboratories (Varian, Inc.) were manufactured by GPC uses The 220 high temperature GPC instruments of PL-GPC of RI detectors, measure the weight average molecular weight being mentioned herein.By about 0.02g polymer samples It is dissolved in containing 250ppm butylated hydroxytoluenes (BHT) and 0.05mol NaNO35ml tetrahydrofurans in (THF).Mildly Ground shakes sample solution about 2 hours, and by making the disposable disk filters of PTFE that sample solution flows through 0.45 micron filter. Chromatographic condition is：Mobile phase：THF with 250ppm BHT and 1.0% acetic acid, 70 DEG C, 1.0ml/min.Sample size：100 is micro- It rises, column setting：PLgel (Guard+2xMixed-C), all 5 microns, series connection.Use Waters Empower Pro LC/GPC Software, analysis result, and calculate the Mw of Inventive polymers.Use polystyrene standards.
Embodiment：
Following embodiments further illustrate the preparation and use of embodiment, but are not intended to limit.It is in specification below The list of the material abbreviations and trade name that use.
Mam Methacrylamides
N-BA n-butyl acrylates
2-EHA 2-EHAs
DEIA diethyl itaconates
TMCHMA methacrylic acid 3,3,5- 3-methyl cyclohexanol esters
DMAEMA methacrylic acids 2- (dimethylamino) ethyl ester
DMAPMA methacrylic acids 3- (dimethylamino) propyl ester
DMAIPMA methacrylic acids 1- (dimethylamino) propyl- 2- bases
Ester
DMABMA methacrylic acids 4- (dimethylamino) butyl ester
DMADMEMA methacrylic acids 2- (dimethylamino) -2- methyl
Propyl ester
DMADMPMA methacrylic acids 3- (dimethylamino) -2,2- two
Methyl propyl ester
The pungent pentyl ester of DMANPA acrylic acid N, N- dimethylamino
- 25 methacrylate of CSEM25 ceteareths
HEMA 2-Hydroxyethyl methacrylate
TEGDMA dimethacrylate Triethylene Glycols
TMPDAE trimethylolpropane allyl ethers
TMPTA trimethylolpropane trimethacrylates
MBA methylene-bisacrylamides
The allyl ether of AS sucrose
The allyl ether of APE pentaerythrites
VEOVA-10 vinyl neodecanoates
VP n-vinyl pyrrolidone
SMA stearyl methacrylates
H2O2Hydrogen peroxide
Polyglykol empirical formulas are CH2=CH
CH2O(C3H6O)4(C2H4O)6The random ethyoxyl of-H
Synthesis DMAPMA or DMADMPMA- passes through transesterification
The first of 2.5 equivalents is added into the reaction flask equipped with distillation column, condenser, thermometer and nitrogen/air intake Base methyl acrylate (MMA), (1.0 equivalent) dimethyl amino propanol (DMAPOL) or 3- dimethylaminos -2,2- dimethyl -1 The suitable transesterification of propyl alcohol (DMADMPOL), suitable polymerization inhibitor, such as phenothiazine or MEHQ and catalytic amount is catalyzed Agent.Suitable catalyst includes, but are not limited to Sn salt, Ti salt, Zr salt and Zn salt.In one embodiment, these are catalyzed Agent includes, but are not limited to stannic chloride, trifluoromethanesulfonic acid tin, chlorination methyl-tin, dibutyltin diacetate, tin, two fourth tin of dichloride, February Two fourth tin of cinnamic acid, two (trifluoromethanesulfonic acid) two fourth tin, dibutyl tin oxide, two fourth tin of dimethanol, two fourth tin of diethanol, oxalic acid two Xin Xi, two pungent tin of dichloride, two pungent tin of tin dilaurate, two (trifluoromethanesulfonic acid) two pungent tin, two pungent tin of oxidation, dimethanol two are pungent Tin, two pungent tin of diethanol, titanium chloride, methanol titanium, titanium ethanolate, isopropyl titanate, butanol titanium etc..Mixture is heated with as mild as a dove Nitrogen/air flowing flow back.It maintains temperature at 100 DEG C -120 DEG C, indicates that reaction is completed until being analyzed by GC.Once Reaction is completed, then can purify required monomer by being evaporated in vacuo, obtain good yield.
About dimethyl amino propanol (DMAPOL) or 3- dimethylamino -2,2- dimethyl -1- propyl alcohol (DMADMPOL), These compounds can be synthesized according to many technologies, including but not limited to, in the US provisional patent Shen that August in 2009 is submitted on the 6th Please No.61/231, those technique/methods disclosed in 780 introduce the disclosure of which by reference of text herein.
Acid base titration：Exemplary method according to the above disclosure synthesizes a series of amine acrylate monomers, and it is steady to test hydrolysis It is qualitative.The hydrolytic stability of these amine monomers is tested, and (referring to Fig. 1) compared with the stability of DMAEMA.Higher acid value Show the aqueous amine solution of higher degree.On the contrary, compared with DMAEMA, there is increased chain length and hydrophobic all other amine to show Go out the hydrolytic stability of higher degree.It was found that by the carbon chain lengths between nitrogen and ester oxygen atom come increase hydrophobicity be reduce water Unexpected factor in solution.Extend at least three carbon atom or 2 carbon originals when the chain length between nitrogen and ester oxygen is replaced by alkyl The period of the day from 11 p.m. to 1 a.m, the branched hydrolytic stability for effectively improving increased chain length.
1H NMR researchs：In order to confirm the performance of DMADMPMA, pass through1H NMR research and applications hydrolytic processes (referring to Fig. 2). Similarly, compared with DMAEMA, DMADMPMA shows excellent hydrolytic stability.
The overall process of polymerization：In typical polymerization, it is suitable included in 2L reactors that monomer mixture is added to To prepare monomer emulsions in the solution for carrying out mixed emulsifying surfactant in the water of amount, the surfactant is for example non- Ionic surface active agent, such as straight chain or branched alcohol b-oxide or nonionic surfactant and anion surfactant Mixture, the anion surfactant such as aliphatic alcohol sulfate or alkylsulfonate, methyl glycoside derivates (GlucamateTMDOE 120,GlucamateTMSSE-20 and GlucamateTMLT).By any suitable method, such as It is then poly- by adding polymerization catalyst (initiator) such as sodium peroxydisulfate or lotion by with nitrogen nitrogen, making lotion deoxidation The well-known any other suitable addition polymerization catalyst in conjunction field, initiated polymerization.It is stirred to react, is completed until polymerizeing, Typically time range is about 4 hours-about 16 hours.Optionally, monomer emulsions can be heated to ranging from about 20 DEG C-about 95 DEG C temperature, add initiator later.Such as emulsion polymerization field it is well known that can be eliminated not by adding more catalyst The monomer of reaction.Then resulting polymers emulsion product is discharged from reactor and packs for storing or using.Optionally, may be used The pH or other physics and chemical characteristic for adjusting lotion, are discharged from reactor later.Typically, total in product emulsion to gather It is about 15wt%- about 60wt% to close object content range, but the total polymer solid (TS) of generally no greater than about 40wt%.
Comparison polymer：The reference material 1- comparison polymers (embodiment 0) are manufactured with the DMANPA of acrylic acid ester amine form. The reference material 2- comparison polymers（Embodiment 18）It is manufactured with DMAEMA.Reference material 3- be based on commercial polymer (Entitled polyacrylate-the 1Crosspolymer of Aqua CC, INCI) DMAEMA.
Table 1 describes the list of new copolymer and its composition.These new polymer use following at least one amine lists Body：DMANPA, DMADMPMA, DMAPMA, DMABMA and DMAEMA and the synthesis of other copolymerisable monomers.Embodiment is used in table 1 The multi-purpose polymer that number 3 indicates is prepared according to above-described overall process, and is then being described in detail.It is stirred in mixing It mixes down, it will about 59.05g ethyl acrylates, about 35g DMADMPMA, about 1.8g HEMA, about 4.0g RAL307 and about 0.15g TEGDMA is added in reactor to prepare monomer emulsions, and the reactor contains the Emulsogen E407 containing about 24.29g (70%) the about 360g water of nonionic surfactant and about 2.0g NaLSs (30%) anion surfactant.In nitrogen Under atmosphere at a temperature of about 40 DEG C of about 30-, stirring gained mixture (about 200rpm), until obtaining lotion.Then, it is mixing Under stirring, by oxidizing agent solution and about 0.12 parts by weight of the about 0.16g sodium peroxydisulfates in about 5g water Reducing agent solutions of the FF6 in about 5g water is added in monomer emulsions with initiated polymerization.After adding initiator, reaction The temperature of mixture maintains the temperature about 2.5 hours of about 70 DEG C of ranging from about 60-.About 1.0 hours peace treaties after initiation reaction At 2.0 hours, and the initiator of additional quantity (for the initiator for each additional quantity added, the pact in about 3.0g water 0.08g sodium peroxydisulfates and the about 0.06g in about 3.0g waterFF6).Reaction temperature maintains about 60- about 70 DEG C additional 2.5 hours with complete polymerization.Then resulting polymers product emulsion is cooled down to room temperature, is discharged and is returned from reactor It receives.Resulting polymers lotion embodiment number 3 has the total polymer solid of about 21wt%, and pH is about 7.79 and viscosity is about 8.5mPa·s.Remaining example monomer component shown in table that table 1 is listed is similarly prepared.
Table 2 provides the performance of latex, such as the TS% of each polymer, viscosity, pH and acid value.Pair containing DMAEMA Show that the monomer of significant quantity in the course of the polymerization process hydrolyzes according to high acid value shown in polymer (embodiment 18).On the contrary, implementing The polymer of example 1,12 and 13 shows lower acid value, shows the polymerization based on DMAPMA and DMABMA in the course of the polymerization process The improved hydrolytic stability of object.However, all other polymer provides much lower acid value, this proves base in the course of the polymerization process In polymer and its blend (DMADMPMA/DMAPMA and DMADMPMA/DMAEMA) preferable hydrolysis-stable of DMADMPMA Property.
Table 3 gives the thickening properties for the polymer that table 1 is listed.(2wt% polymer is solid in deionized water for 2%TS gels The mucus (mucilage) of body total weight) it is prepared by being neutralized to pH4.0 with 50% hydrous ethanol acid, then characterize its viscosity (20RPM), YV, pH and clarity (with the turbidimetry in NTU).
Compared with methacrylate forms (embodiment 1,2, the polymer of 2a, 3,12 and 13), prepared with DMANPA Comparison polymer (embodiment 0) shows poor at 2%TS (mucus of the total polymer solid of 2wt% in deionized water) Thickening properties.
The performance of table 2- latex
* comparative examples
* TS=total polymer solid
Table 3- thickening properties
* comparative examples
* is with 50:50(wt./wt.)H2O/ glycolic lotions neutralize the 2wt.% polymer solids mucus to pH4.
Hydrolytic stability：
In ageing research as described below, it was demonstrated that manufactured with the amine monomers (DMAPMA and DMADMPMA) of hydrolysis-stable Multipurpose copolymer improved storage life performance.
This research carries out under different conditions at three, such as：(1) latex is stored at 45 DEG C 3 months；(2) at 50 DEG C Store latex 5 weeks；(3) in room temperature storage latex 1- about 2 years.
In the ageing research (storing latex at 45 DEG C 3 months) for increasing temperature：
Two kinds of polymer (Examples 1 and 2) is stored in 45 DEG C of baking oven 3 months.Sample is periodically taken out, and tests glue The performance and its thickening properties of breast (referring to table 4).Fig. 3 provides the acid value indicated with mg KOH/g (acid value) to latex at 45 DEG C All numbers of lower storage.It is excellent that both polymer all show that moderate (DMAPMA monomers) arrives under the condition of storage of 45 DEG C of temperature The storage life performance of (using DMADMPMA monomers).
The thickening properties of table 4- aged samples (3 months at 45 DEG C)
By being neutralized to pH4 with 50% glycolic, 2% gel is prepared by the polymer of aging.Lower Fig. 4 is provided 2% gel viscosity (mPas) is to time (all numbers that latex is stored at 45 DEG C).
Ageing research (at 50 DEG C 5 weeks) at elevated temperature：
Two kinds of polymer (embodiment 4 and 7) is stored in 50 DEG C of baking oven 5 weeks.Sample is taken out weekly, and tests latex Energy and its thickening properties (table 5).Fig. 5 provides the acid value of the two kinds of polymer using DMADMPMA synthesis indicated with mg KOH/g To time (all numbers that latex is stored at 50 DEG C).Similarly, Fig. 6 shows two kinds of polymer and the control of embodiment 4 and 7 The TS gel viscosities of 2% wt% of object 3 are to the time.The two figures prove the acid value and viscosity point in 50 DEG C of stabilizations at any time Cloth, it was confirmed that with the polymer that DMADMPMA monomers manufacture compared with reference material 3 better hydrolytic stability.
Table 5 shows that multi-purpose polymer does not decline in 50 DEG C of good stability and noticeable thickening effectiveness, This is opposite with the reference material 3 for stablizing deterioration of thickening effectiveness is shown under the same conditions.
Table 5- aged samples thickening properties (50 DEG C 5 weeks)
Product colour：
Typically, become brown from milky in room temperature (RT) or 45 DEG C of reference materials 3 stored.However, by DMADMPMA Monomer manufacture multi-purpose polymer (embodiment 4 and 7) before and after raised temperature (such as 50 DEG C) stores with compared with Good colour stability.
It is studied in room temperature 1-2 annual agings：
The stability of 8 kinds of polymer (embodiment 1,2,4,6,7,8,13 and 14) and reference material 3 is monitored, and tests them About 9 months to about 1 year performances.It periodically takes out sample and tests latex performance and thickening properties.Fig. 7 shows acid value clock synchronization Between (months of the latex in room temperature storage).All these polymer (20 DEG C -25 DEG C) under ambient room temperature condition of storage are shown Moderate (embodiment 1,2,13 and 14) arrives the storage life performance of excellent (embodiment 4,6,7 and 8).On the contrary, in room temperature storage condition Under, reference material 3 undergoes the increase that acid value is stablized, and shows that DMAEMA skeletons are gradually degraded.
Fig. 8 shows thickening (2% gel) performance of the polymer based on DMADMPMA monitored through about 2 annual periodicities of 1-. All 4 kinds of polymer (embodiment 4,6,7 and 9) show stable performance, show the good storage life of these polymer, and right It is gradually degraded in the meantime due to its DMAEMA skeleton according to the performance of object 3.
Table 6 provides the latex (wt%TS, pH, viscosity and acid value) and 2% gel of several multi-purpose polymers of the present invention Performance (viscosity, YV and turbidity).These performances are tested through about 2 annual periodicities of 1-.Usually, based on the new of DMADMPMA monomers Polymer has passed through storage life research in 1 year in experimental error.Table 6, which is also provided, to be blended through what 1 annual periodicity monitored based on amine The thickening properties of the polymer (embodiment 14 and 15) of object (DMADMPMA/DMAEMA).Polymer example 14 and 15 contains respectively There is about 25% and 50% DMAEMA.Both polymer showing in terms of their thickening properties slightly decreases, but still So it is better than the reference material 3 gradually degraded.The thickening properties of polymer (Examples 1 and 2) based on DMAPMA show most 6 The stability of the moon, then at 10th month, viscosity slightly decreased, but still was better than reference material 3.
Typically, slowly become brown from milky in the product of the reference material of room temperature storage 3.On the contrary, by DMAPMA Or the polymer of the present invention of DMADMPMA monomers manufacture has preferable colour stable under the conditions of room temperature storage after 1 year Property.
Table 6-1 storage life researchs：The thickening properties of polymer
* RT=ambient room temperature (about 20-25 DEG C)
* is with 50:50(wt./wt.)H2O/ glycollic acid solutions neutralize the 2wt.% polymer solids mucus to pH4.
Quaternary polymers
The multi-purpose polymer of embodiment 45 and 46 shown in table 8 is prepared, then using dithyl sulfate about 60 DEG C of seasons Change (theoretical value of 50% quaternary degree).Both quaternary polymer are all drumped, and viscosity is 670 and 1,880mPa s.Turbidity is respectively 160 and 248NTU.
Table 8- compositions
Amine oxide polymer-solution polymer
Prepare amine copolymer object (embodiment 47-50) using DMADMPMA as comonomer, and using hydrogen peroxide by it Be converted to their amine oxide, and compared with the amine oxide polymer based on DMAEMA.DMADMPMA polymer is molten The acid value lower than DMAEMA is obtained in liquid polymerization.Low acid value shows the preferable hydrolytic stabilities of DMADMPMA.Table 9 is shown often The composition details of one polymer.
The composition of table 9- amine oxide polymer

Claims (18)

1. a kind of polymer is the reaction product of the polymerization comprising monomer mixture below：
(i) mixture comprising (a), (b) and (c),
(ii) mixture comprising (a), (b) and (d),
(iii) mixture comprising (a), (b) and (e),
(iv) mixture comprising (a), (b), (c) and (d),
(v) mixture comprising (a), (b), (c) and (e),
(vi) mixture comprising (a), (b), (d) and (e), or
(vii) mixture comprising (a), (b), (c), (d) and (e),
Wherein monomer component (a) is that at least one amino replaces (methyl) acrylate (ASMA) monomer or its salt, monomer group It is at least one non-ionic vinyl (NIV) monomer to divide (b), and monomer component (c) is that at least one vinyl association (VA) is single Body, monomer component (d) are at least one vinyl surfactant (VS) monomers, and monomer component (e) is at least one polymerizable Siloxane macromer (PSM) and any of which said mixture optionally further contain：(f) at least one crosslinking (XL) monomer, (g) at least one chain-transferring agent (CTA), (h) at least one polymer stabilizer or component (f), (g) and/or (h) any suitable combination of two or more in, wherein monomer component (a) are selected from methacrylic acid 3- (dimethylaminos Base) -2,2- dimethyl propyl ester, their salt or their mixture.
2. at least one that the polymer of claim 1, wherein monomer component (b) select free style (III) and (IV) to indicate can be total to Poly- non-ionic ethylenically unsaturated monomers：
C(X)2=C (X) Z (III)
CH2=CH-OC (O) R1 (IV)
Wherein in each formula (III) and (IV), each X independently is hydrogen, methyl ,-CH2C(O)OR1、-C(O)OR1；It is-C (O) with Z OR1、-C6H4R1、-C6H4OR1、-CN、-C(O)N(R1)2、-NHC(O)CH3、-NHC(O)H、-C(O)OA'OR15, N- (2- pyrrolidines Ketone group), N- caprolactams base ,-C (O) NHCH2CH2- N- ethylidene-ureas or-C (O) NHC (CH3)3；A' is to be selected from-CH2CH(OH) CH2And-CH2CH(CH2OH)-bivalent group, each R1It independently is straight chain and branched C1-C30The C that alkyl, hydroxyl replace2- C30Alkyl, C5-C30Naphthenic base and C1-C5Alkyl-substituted C5-C30Naphthenic base；R15It is straight chain or branched, saturation or unsaturated C6-C22The acyl residue of aliphatic acid.
3. the polymer of claim 2, wherein monomer component (b) are selected from least one (methyl) acrylic acid C1-C30Arrcostab, extremely Few one kind (methyl) dihydroxypropyl C2-C30Arrcostab, at least one C1-C30Alkyl (methyl) acrylamide, styrene, at least A kind of substituted styrene, at least one vinyl acetate, at least one undersaturated nitrile, tertiary capric acid ethylene oxidic ester and acrylic acid Any group of reaction product, the reaction product of tertiary capric acid ethylene oxidic ester and methacrylic acid or two or more in them It closes.
4. the polymer of claim 2, wherein monomer component (b) are selected from methyl acrylate, ethyl acrylate, methyl methacrylate Ester, n-butyl acrylate, 2-EHA, methacrylic acid 3,3,5- 3-methyl cyclohexanols ester, methacrylic acid are stearic Ester and in them any two or more suitable mixture.
5. the polymer of claim 1, wherein monomer component (c), which are selected from, has following at least one monomers：(A) it is used for and list The ethylenic bond unsaturation terminal portion of other monomer addition polymerizations in body mixture；(B) it is used to assign resulting polymer selectivity parent The polyoxy alkylidene middle section of aqueous energy；(C) is used to provide the hydrophobic terminal portion of selective hydrophobic performance for polymer.
6. the polymer of claim 1, wherein monomer component (c) are selected from at least one monomer indicated by lower formula (V)：
Wherein each R2It independently is H, methyl ,-C (O) OH or-C (O) OR3；R3It is C1-C30Alkyl；A is-CH2C(O)O-、-C(O) O- ,-O- or-CH2O-；(R4-O)nIt is polyoxy alkylidene, is C2-C4Homopolymer, the random copolymer of oxygroup alkylidene unit Or block copolymer, wherein each R4It independently is C2H4、C3H6、C4H8Or they mixing and n be integer of the range in 5-250； Wherein R5Selected from substituted or unsubstituted straight chain or branched C8-C40Alkyl, C8-C40Carbocyclic ring alkyl, C2-C40It is alkyl-substituted The C that phenyl, aryl replace2-C40Alkyl and C8-C80Mixed ester, wherein the C8-C80Mixed ester is selected from rilanit special, 1,2- Distearyl glyceride, 1,2- palmityls glyceride, 1,2- myristyls glyceride, tri- stearyls of glucose 3,4,6-, Fructose 2,3- dilauryls ester and sorbitol ester, wherein R5Alkyl optionally includes selected from hydroxyl, alkoxy or halogen group One or more of substituent group.
7. the polymer of claim 1, wherein monomer component (c) are selected from cetyl polyethoxylated methacrylate ester, whale The stearyl polyethoxylated methacrylate of wax, stearyl polyethoxylated (methyl) acrylate, the poly- ethoxy of eicosyl Base (methyl) acrylate, docosyl polyethoxylated methacrylate ester, lauryl polyethoxylated methyl propylene Acid esters, cerul polyethoxylated (methyl) acrylate, octacosyl polyethoxylated (methyl) acrylate, three Ten alkyl polyethoxylates (methyl) acrylate, dotriacontyl polyethoxylated (methyl) acrylate, triphenylethylene base Phenol polyethoxylated methacrylate ester, rilanit special polyethoxylated methacrylate ester, rapeseed oil polyethoxylated It is one or more in (methyl) acrylate and cholesterol polyethoxylated methacrylate ester, the wherein poly- second of the monomer Oxygroup part includes 5-100 ethylene oxide repeating units.
8. the polymer of claim 1, wherein monomer component (d) select at least one monomer that free style (VI) indicates：
Wherein each R6It independently is hydrogen or methyl ,-C (O) OH or-C (O) OR7；R7It is C1-C30Alkyl；A is-CH2C(O)O-、-C (O) O- ,-O- or-CH2O-；It is 0 or 1 that p, which is range in the integer and r of 0-30, and condition is that r is 0 when p is 0, and when the model of p R is 1 when being trapped among 1-30；(R8-O)vIt is polyoxy alkylidene, is C2-C4Homopolymer, the random copolymer of oxygroup alkylidene unit Or block copolymer, wherein each R8It independently is C2H4、C3H6、C4H8Or they mixing and v be integer of the range in 1-250； And R9It is hydrogen or C1-C4Alkyl.
9. the polymer of claim 1, wherein monomer component (d) are selected from least one monomer with one of following chemical formula：
H2C=CH-O (CH2)aO(C3H6O)b(C2H4O)cH；
H2C=CHCH2O(C3H6O)d(C2H4O)eH；
H2C=C (Q)-C (O)-O (CH2)aO(C3H6O)b(C2H4O)cH；
Or H2C=C (Q)-C (O)-O (C3H6O)d(C2H4O)eH wherein Q are hydrogen or methyl；A is 2,3 or 4；B is range in 0 or 1- 10 integer；C is integer of the range in 0 or 5-50；D is integer of the range in 0 or 1-10；It is range in the whole of 0 or 1-50 with e Number, wherein b and c, which can not be 0 and d and e simultaneously, to be 0 simultaneously.
10. the polymer of claim 9, wherein b or c can be 0.
11. the polymer of claim 9, wherein d or e can be 0.
12. the polymer of claim 1, wherein monomer component (e) are selected from at least one polymerizable siloxane being expressed from the next Alkane macromonomer：
Wherein each R20Independently selected from straight chain or branched C1-C30Alkyl, C4-C20Aryl or C2-C20Alkenyl；Wherein (R8-O)v It is polyoxyalkylene group, it can be with C2-C4The homopolymer of oxygroup alkylidene unit, random copolymer, block copolymer row Row, wherein each R8It independently is C2H4、C3H6、C4H8Or they mixing and v be integer of the range in 1-250；X is that range exists The integer of 0-200；Y is integer of the range in 0-200；It is integer of the range in 1-200 with z；Wherein G is selected from containing at least Any structure division of the carbon-carbon double bond of one free redical polymerization.
13. the polymer of claim 1, wherein monomer mixture further include component (f), and based on the total of monomer mixture Weight meter, component (f) exist with the range of 0.001wt%-5wt%.
14. the polymer of any one of claim 1-13, wherein the polymer is by being selected from comprising (a), (b) and (d) (ii) monomer mixture polymerization, wherein monomer component (a) are selected from methacrylic acid 3- (dimethylamino) -2,2- dimethyl propylenes Ester；Monomer component (b) is selected from (methyl) acrylic acid C1-C30The C that Arrcostab, (methyl) dihydroxypropyl replace1-C30Arrcostab, And their at least one of mixture；It is selected from at least one monomer being expressed from the next and its mixing with monomer component (d) Object, the wherein range of d are in the range of 1-20 and e in 5-40：
H2C=CHCH2O(C3H6O)d(C2H4O)eH。
15. the polymer of claim 14, wherein the polymer is by including methacrylic acid 3- (dimethylamino) -2,2- bis- Methyl propyl ester, ethyl acrylate, methyl acrylate and by following formula H2C=CHCH2O(C3H6O)2-10(C2H4O)10-25The list that H is indicated The monomer mixture of body polymerize.
16. the polymer of claim 1, wherein the polymer is mixed by the monomer for being selected from (i) comprising (a), (b) and (c) Object polymerize, and wherein monomer component (a) is selected from methacrylic acid 3- (dimethylamino) -2,2- dimethyl propyl ester；Monomer component (b) Selected from (methyl) acrylic acid C1-C30At least one of Arrcostab and its mixture；It is selected from the following at least with monomer component (c) A kind of monomer：Cetyl polyethoxylated methacrylate ester, cetearyl polyethoxylated methacrylate ester, stearyl Polyethoxylated (methyl) acrylate, eicosyl polyethoxylated (methyl) acrylate, docosyl polyethoxy Change methacrylate, lauryl polyethoxylated methacrylate ester, cerul polyethoxylated (methyl) acrylic acid Ester, octacosyl polyethoxylated (methyl) acrylate, melissyl polyethoxylated (methyl) acrylate, 32 Alkyl polyethoxylate (methyl) acrylate, triphenyl vinyl phenol polyethoxylated methacrylate ester, rilanit special Polyethoxylated methacrylate ester, rapeseed oil polyethoxylated (methyl) acrylate and cholesterol polyethoxylated methyl It is one or more in acrylate, wherein the polyethoxylated part of the monomer, which includes 5-100 ethylene oxide, repeats list Member.
17. personal care product, health care products, household care products, public organizations' care product or industrial nursing product, Include the polymer of any one of claims 1-16.
18. the polymer of any one of claim 1-16 as improve chemistry and physiologically active ingredient and cosmetic efficiency, Deposition or the emulsifier of delivering, stabilizer, suspending agent, deposition aid, film forming agent, thickener, rheology modifier, Hairsetting Agent adjusts setting agent, conditioner, and humidizer sprawls auxiliary agent, carrier, and the preparation that they are contained within as improvement The reagent of physiological sensing and aesthetic properties, or as antistatic agent, biocide, bacteriostatic agent, preservative and antimicrobial Purposes.
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